sare OCT 4

NBS

/"\ i i iv 1 1 v

Compendium of ab initio

Calculations of Molecular

Energies and Properties

438

*** OF

,*

\ n

U.S. DEPARTMENT OF COMMERCE

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NBS TECHNICAL NOTE 438

ISSUED DECEMBER 1967

Compendium of ab initio Calculations of

Molecular Energies and Properties

Morris Krauss

Physical Chemistry Division

Institute for Basic Standards

National Bureau of Standards

Washington, D.C. 20234

This work was supported by the

Advanced Research Projects Agency of the

Department of Defense under Project DEFENDER.

NBS Technical Nqtes are designed to supplement the Bureau's regular publications program. They provide a means for making available scientific data that are of transient or limited interest. Technical Notes may be

listed or referred to in the open literature.

For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C, 20402

Price 70 cents.

Table of Contents

Abstract 1 A. Preface 2 B. Annotated Bibliography

I nt roduction 5 Glossary 6

HeH 9 HeH 9 LiH+

, LiH 10

BeH

+

, BeH 10

BH+

, BH 11

CH+

, CH, CH" 11

NH+

, NH 12

NH", 0H+

, OH 12

OH", HF+

13

HF 13

NeH+

, NaH+, NaH 14

MgH+

, MgH, A1H+

14

A1H, SiH+

, SiH 15

SiH~, PH+

, PH 15

PH", SH+

, SH 16

SH~, HC1+

16

HCl 17

He^, He

2+

17

He

2 18

Li

2+

, Li

2 18

Be

2

, B

2 19

C

2 19

N

2+

, N

2 20

°2> °2 2 °

IE
Table of Contents

-

} p

2+

21

F

2

, p

2

" 21

Ne

2+

, Ne

2 22

Na

2

, Mg

2

, Al

2

, Si

2 22

P

2

, S 2

, Cl

2+

, Cl

2

23

Cl

2

, Ar

2

, Ar

2 23

HeLi , HeLi, HeO 24

HeF, HeNe

+

, HeNe, HeAr 24

LIB, LiC, LiN 25

LiO

+

, LiO, LiF 25

LiF

+

, LiNa, LiCl 26

LiBr, BeO 26

BeO, BeF , BeF, Be Ne— 27

BeS, BN

+

, BN 27

BO , BO, BO" 28

BF, BF 28

CN

+

, CN, C0

+

29

CO, CF

+--- 29

CF, CS, NO+

30

N0 3 NeO, NeF, NeAr 30

NaF, NaCl, NaBr 31

MgO, MgF, A1F 31

SiO, PN, PO 32

P0~, C1F, KF, KC1 32

CaO, ScO, ScF 33

TiO, VO 33

RbF, SrO 34

H

3+

4

H

3

, HeH

2

, LiH

2

" 35

IV
Table of Content s

BeH2? BH* BH~ — - --- --- 35

CH

2

, NH*- - - —-36

NH

2

, NH~, H

2 + - - -- 36

H

20, H2 F+

- 37

H

2 F", NeH2

, H

2

S 37

Li H+

, Li H~ - 38

2 ' 2 LiOH, HCN, FOH - —- 38

FHF~, HeF

2

, Li

2 0, BeF^ C

3 39

NeC , OCN~, FCN, SCN~, C1CN 39

C0

2

, ScO, H", N

20, NeN2

- 40

NO* N0~, NF+

40

3

, Ne0

2

, F

2

- 41

NeF 41

H+ H BeH" 41

BH„,*3 ; CH_ 42

CH

3

, CH

3

, CF

3

42

NH* NH - --- 43

HO+

, PH., HCCH - 43

HCCH, HCHO 44

HO LiCCH, FCCH, C1CCH - 44

HCOF, (CN)

2

, NF

3— 45

BH4, CH4

- - 45

NH

+

, PhI", SiR* - - - --- 46 4' 4 4
Table of Contents

Chronological References 47

Experimental and Hartree-Fock Atomic Energies 58

Atomic Unit Conversions 59

C. One-electron Properties: DIpole Moment and Derivative, Quadrupole

Moment, Field Gradient.

Introduction 60

H , LiH 61

BeH, BH, CH 61

NH, OH 62

FH, NaH, MgH 62

A1H, SiH, PH, SH, C1H 63

He

2

, U

2

, B

2

, C

2

, N

2 63

N

2

, 2

, F

2

, Na

2

64

LiF, LICl, LiBr, BeO 64

BF, CO 65

CS, NaF, NaCl, NaBr 65

MgO, A1F, SIO, PN, C1F 66

KF, KC1, CaO, ScO 66

ScF, TIO, RbF, SrO 67

H

20, H

2

S, HCN 67

FHF", OCN", CO , N

20, FCN 68

SCN", SCO, C1CN, NH , C^ 68

LICCH, HCCF, HCCC1, NCCN 69

HCCCN 69

VI
Table of Contents

Static Polarizabilities

Introduction-- 70

H

2

, LiH, HP, F

2

, N

2

, CO, Ug, BF- —

70

HP, HC1, LiF, BF — ----- 71

CO, NaBr, KC1, RbF 71

A1F, SiO, PN, SrO - --- - 71

HCN, NO, 0CN~, FCN, SCO 71

SCN~, C1CN, FCCH, C1CCH—

- 71

NCCCH - - 71

Magnetic Constants

Introduction . 72

LiH, Li

2

, FH, F , BH - 72

Spectroscopic Constants

Introduction-- 73

H

2

- 73

HeH

+ - --- 74

HeH, LiH, BeH, BH, CH 74

NH, OH, OH", HF, NaH - 75

MgH, A1H, SiH, PH, SH, HC1 75

He

2+

, He

2

, Li

£

, C

2

- 76

N

2

+ - 76

N

2

, F

2

, F

2

, Ne

2+

, Cl

2

77

Cl

2

", Ar

2+

- 77

HeLit HeLi, LiF, LiNa - - - 78

LiCl, BeO, BN - - 78

BF, CO, NaF - - - - 79

NaCl — 79

MgO, ScO, ScF-- « - 79

TiO - 80

H

3+ - - —- 8 ° AH„- - - 80

VII
Table of Cont ent

s

G. Dissociation Energies: Diatomics

Introduction 81

Hydrides: Li, Be, B, C, N, 0, F, 81

Na, Mg, Al, Si, P, S, CI 81

Homonuclear: He , Li„ , B„ , C

?

, N , 82 + ,2 + 2 3_i i +

N

2

( ^ g> n

u

>> °2

^ g

> A

g

, S ), 82

F , F ~, Ne , Na 82

2

' 2' 2' 2 CI , CI ', Ar +

82

Heteronuclear: HeLi, LiO, LiF, LiNa, 83

LiCl, BeO, BeF, BF, BO, CO, NO, 83

NaF, NaCl 83

H. Electron Affinities

Introduction 84

CH. NH, OH, SiH, PH, SH, NO

I. Orbital Energies

Introduction 85

Homonuclear diatomic:

H2 , Li2 , B2 , C2 , N2 — 85

°2 > °2~> F

2 ' Na2 86

Heteronuclear diatomic

LiB, LiC, LiN, LiO 86

LiF, LiNa, LiCl, LiBr -87

BeO, BeF, BO 87

B0~, BF, CN, CO 88

CF, CS, NO, NaF 88

NaCl, NaBr, MgO, A1F --89

SiO, PN, C1F, KF 89

KC1, CaO, RbF, SrO ---- 90

VIII
Tab le of Contents

Linear triatomic

LiOH, FHF", C OCN" 90

FCN, SCN~, C1CN, CO 91

BeF

2

, SCO, N~, Li

2 91

Non-linear triatomic

FOH, N0~,

3

, F

2 92

AH

2 BH~, CH , NH~, H

2

0, ^S 92

Linear tetratomics, D ,

C

2H

2 ,C

2N2 93

Linear tetratomics, C

' 00V LiCCH, FCCH, C1CCH 93

AH

BeH^, BH

3

, CH

3

, CH^ - -- 94

NH PH 94

AH

4 BH" CH, 94

4 4

J. Energy and Properties as a Function of the Internuclear Distance

Int roduc tion 95

LiF - 95

LiCl -- - 96

BeO 96

BF 97

GO 97

NaF 98

NaCl 98

MgO 99

A1F 99

SiO 100

PN - 100

CaO 101

SrO 101

IX
Table of Contents

K. Potential Energy Curves

Introduction 102

H

2 102

HeH 103

HeH 103

LiH, BeH 104

BH, CH 104

NH, OH 105

HF 105

NaH, MgH 106

A1H, SiH 107

PH, SH 108

HC1-- 108

NeH t 109

He +

Li

2 m

2 m

F

2 112

F

Ne

+

2 113

+

Ar

2 113

01

2 114

CI"

2 115

HeNe_ 1X5

NaLi 116

NaF 116

BeH

2 „_. n7

HCN 117

N

2 — 118

H2 F 119

X
Table of Contents

Figures and Acknowledgements

Figure Acknowledgement

1 BH — Allen, L. C. (1966), "Quantum Theory of Atoms, Molecules,

and the Solid State", Edited by P. 0. Lowdin (Academic Press

Inc. , New York)

.

2,3 He-He; Ne-Ne — Gilbert, T. L. and Wahl, A. C. (1967), "Singleconfiguration wave functions and potential curves for some diatomic systems. I. The ground state of He_, Ne , and Ar .

Scheduled to be published.

4 HeNe, HeAr, NeAr — Matcha, R. L. and Nesbet, R. K. (1967),

"Electric dipole moments of rare gas diatomic molecules."

Scheduled to be published.

5 Li — Das, G. (1967), J. Chem. Phys. 46_, 1568.

6 B — Bender, C. F. and Davidson, E. R. (1967), J. Chem. Phys.

4_i5, 3313.

7 C. — Fougere, P. F. and Nesbet, R. K. (1966), J. Chem. Phys.

44, 285.

8 N

2

, N + — Cade, P. E., Sales, K. D., and Wahl, A. C. (1966),

J. Chem. Phys. 44, 1973.

9 F — Harris, F. E. and Michels, H. H. (1967), "Open-shell

valence configuration-interaction studies of diatomic and

polyatomic molecules" to be published Int. J. Quant. Chem.

Slater Symposium Issue.

10,11,12 F

2

; LiNa; NaF — Wahl, A. C, Bertoncini, P. J., Das, G., and

Gilbert, T. L. (1967), "Recent progress beyond the Hartree-Fock

method for diatomic molecules: The method of optimized valence

configurations." To be published Int. J. Quant. Chem. Slater

Symposium Issue.

13 H — Conroy, H. and Bruner, B. L. (1966), "Molecular schrodinger

equation VT. Results for H_ and other simple systems."

Mellon Institute Preprint No. 22.

XI
Figure Acknowledgement

14 H,j — Edmiston, C. and Krauss, M. (1967), unpublished results.

15,16 C

2

H6' m3 m — Fink, W. H. and Allen, L. C. (1967), J. Chem.

Phys. 46_, 2261.

17 NH.C1 — Clementi, E. (1967), "Study of the Electronic Structure

of Molecules. II. Wavefunctions for the NH + HC1 -* NH.C1

Reaction." IBM Research Report RJ411.

L. Survey of Large Gaussian Basis Calculations

Introduction 128

C H, 128

Z b

B

2H6

129

C

2H

4

129

S

H

6

130

C

4

H

2 130

C.H, -131

4 6

H

2

C0 132

CH

3

N0, CH

2 2 132

CH

3

F 133

C

2H

5F 133

C

4

H

5 N, Pyrrole 134

C-H_N, Pyridine 135

C.H.N , Pyrazine 136

Li C

5H5 137

C,H. 137

6 6 / / /

Acknowledgement 138

XII
COMPENDIUM OF ab initio CALCULATIONS OF

MOLECULAR ENERGIES AND PROPERTIES

ABSTRACT

The number of ab initio molecular electronic calculations has

increased dramatically in the last few years. Both the practitioners

and other interested students of the results of the calculations have

found it increasingly difficult to determine the present status of

these calculations. This compendium references the work from 1960 to

the present and abstracts from the mass of data the best values for

several observable properties including the total energy, dissociation

energy, electron affinity, spectroscopic constants, electric moments,

field gradients, polarizabilities, and magnetic constants. In order

to provide an insight into molecular electronic structure tables of

orbital energies are also included.

These tables are meant to direct attention to the successes and

failures of the calculations by compiling a large percentage of the

best results in a reasonably compact form. Its usefulness will be

limited in time by rapid advance in the field.

KEY WORDS: ab initio electronic calculation, molecular electronic

structure, energy, dissociation energy, dipole moment,

quadrupole moment, polarizability, electron affinity,

field gradient, spectroscopic constants, magnetic

constants, orbital energy.
A. Preface

The increasing accessibility of powerful digital computers has inspired

many investigators to the calculation of accurate electronic energies and

other properties for molecules. In recent years a sufficient number of ab

initio calculations have been completed to provide the evidence of the successes and failures of the variational techniques that form the bulk of

the calculations. I do not believe the range of these calculations is widely

known. This compendium is an effort to provide the non-specialist with an

insight into the results that have been obtained to date as well as to

summarize a wide range of data for the specialist.

This compendium will reference the variational calculations and will

abstract from the more accurate calculations the values of certain observables

e.g. the total energies, electric moments, field gradients and orbital energies.

It is not our intention to critically review this material in any way. Several

recent studies already provide that service. 3 This compendium is intended to

supplement the present and, perhaps, future reviews by providing a selected

compilation of the raw material of the accurate calculations.

Much unpublished material has been included. Indeed without the 1967

references this report would be significantly shorter. It is hoped that the

papers will soon be published so that the full content of this work will be

available. In order to assist the reader to access this information, the address

of the authors of unpublished material is given.

The calculations have been assigned to two broad groups: 1. Hartree-Fock

(H.F.) and 2. Beyond Hartree-Fock. This division and the imputation of

superiority to the second category refers only to the conceptual approach.

In the latter the dynamical electron interaction is in some fashion taken into

consideration. Often, though, the energy for the H.F. approximation is the

lowest obtained for a given molecule; but the energy is not an absolute criterion

of value. Listing the advantages and disadvantages of the H.F. approximation

will suffice to show why certain information was tabulated.

The Hartree-Fock approach is important for the following reasons:

1. At the equilibrium geometry the H.F. function dominates the wave function.

In near degeneracy cases electron correlation must be considered but for many

systems the H.F. function describes the electronic behavior and electrons can

be associated with a given spatial orbital. The orbital energies determine the

spectroscopy of the molecule and the coefficients tell us much of the bonding

properties of the orbital.
2. Expectation values of one-electron operators are good to second -order

(often within 10% of experiment) when perturbed by the correlation potential.

This holds for the perturbation by external fields* 3. Hartree-Fock energies

provide a basis for determining correlation energies empirically and systematic

calculations lay the basis for semi -empirical estimation of correlation energies.

The major disadvantages of the Hartree-Fock approximation are

1. Correlation error is significant for the energy of dissociation, excitation,

and ionization or detachment. 2. Asymptotic behavior of the potential surface

is poor except in exceptional cases involving closed shell fragments. This

behavior reflects itself in appreciable, 20% - 50%, errors in the spectroscopic

constants.

Each section will be preceded by a description of the tables. Table B is an annotated bibliography of ab initio calculations. Tables C, D, E, and F

include selected results for, respectively, the one-electron properties such

as the moments and field gradients, the static polarizabilities, the magnetic

constants, and the spectroscopic constants. Dissociation energies, electron

affinities, and orbital energies are found, respectively, in Tables G, H, and

I. In order to illustrate the range of the data generated by the calculations

the energy and properties as a function of internuclear distance are given in

Tables J and K. Table L very briefly illustrates the rapidly increasing area of polyatomic calculations based upon Gaussian-type basis functions.

It is hoped that the numbers are sufficient witness to the successes or failures of the present techniques and that outside of writing a book on the

subject the less commentary the better,

a. See:

Nesbet, R. K. "Approximate Hartree-Fock calculations on small

molecules" which will appear in Adv. in Quantum Chemistry, ed.

P. 0. Lowdin, Academic Press, N. Y., 1967, Vol. 3; Wahl, A. C,

Bertoncini, P. J,, Das, G., and Gilbert, T. L,, "Recent progress

beyond the Hartree-Fock method for diatomic molecules" which will

appear in the Int. J. of Quantum Chem. 1, 0000 (1967).

B. Annotated Bibliography : Introduction

This section attempts to summarize ab Initio molecular energy calculations from 1960 to the present including many unpublished results. The molecules

are organized in the following order: hydrides AH; homonuclear A ; hetero- nuclear AB; trlatomics AH , ABH, ABC; tetratomic AH , ABH , ABCH, ABCD; pentatomic AH. . A, B, etc. are selected in the periodic table order with A <

B < C < D or in the periodic table order of the first element to appear In the usual chemical nomenclature. In addition to the reference and the state of the molecule (note that the state Is often not repeated when subsequent references refer to the same state) a very brief description of the method and results

are given. The Description of Method Is minimal. A single symbol will denote a wide

variety of calculations which are of unequal significance. The explanatory

symbols which are listed in the glossary refer to the' basic technique of the calculation but there is little or none of explanatory detail. Similarly the Basis Set column Is devoid of detail; the use of the word "Extend." to denote

a basis set larger than the minimum of one function per atomic orbital is per- haps overused since sets of almost minimal as well as saturated character will

be similarly characterized. In most cases the energy, E, is given at a distance,

R, and permits some judgment. For the polyatomic molecules the angles and distances are listed in the most compact form as given in the reference. This may

not be completely unambiguous but consideration of the molecular symmetry and

the convention of listing the internuclear separations in the order given in the formula heading should mitigate any difficulties. Again we note that the ref- erences are pointers only and the details suffer. In this section E and R are

in atomic units.

The column, P, notes the properties considered in this calculation. Since many unpublished calculations are listed, it may happen that the results when

published will be in separate papers. It can also be noted that Hartree-Fock

results from the Laboratory of Molecular Structure and Spectra at the University

of Chicago include all one-electron properties but the references are, in some

cases, to published results which do not include these values. This situation may be more prevalent as computer packages for one-electron properties are being

widely disseminated. In particular note that the Quantum Chemistry Program

Exchange at Indiana University is distributing such a package as QCPE 103 written

by T. Janiszewski and A. C. Wahl.

The check in the column E(R) indicates that a portion of the potential

curve or surface has been calculated.

In order to facilitate a rapid judgment of the accuracy of a calculation a table of ground state H.F. atomic energies that was given by E. Clementi(Tables

of Atomic Functions, Supplement to IBM J. Res. Develop. 9. 2 (1965)) and experimental values recommended by Cade and Huo (1967a, b) is also included after

the references. A table of the conversion factors for the atomic units is also given.

a. See: "Hartree-Fock Wave Functions for Diatomic Molecules AH, A , and AB" Compiled by P. E. Cade to be published last quarter 1967.
Glossary

Hartree-Fock Refers to restricted H.F. as proposed by Roothaan. Indicates close approach to the H.F. energy limit. Nesbet Refers to equivalence and symmetry restriction variant of the H.F. method

SCF Self-consistent field restricted H.F. MO Molecular orbital (signifies calculation of the energy of a state using the unoccupied MD ' s of an SCF calculation) SOC Superposition of configurations

VB Valence bond

NO Natural orbital

Valence Refers to configurations arising only from excitation of valence orbitals

IS Ionic states

DOi^S Different orbital different spin OC One center

STF Slater type function ETF Elliptic type function

GTF Gaussian type function BA Best atom basis

BI Best ion basis

DZ Double zeta basis BA + P Best atom plus polarization basis

E Energy in atomic units

R Internuclear distance in atomic units

T Term values; excited state energies

ID Spectroscopic constants H Dipole moment

Q Quadrupole moment

q Field gradient

P Polarizability

I. Octupole moment Vib-rot Nuclear Schrodinger equation is evaluated

I Ionization potential EA Electron affinity
Reference State Description of Method E(R)

H„

Davidson (1961)

Fraga and Ransil (1961b)

Davidson and Jones (1962a)

Davidson and Jones (1962b)

Bishop (1963)

Harris and Taylor (1963)

Hagstrum and Shull (1963)

Taylor (1963a)

Kolos and Wolniewicz (1963)

Kolos and Wolniewicz (1964a)

Kolos and Wolniewicz (1964b)

Browne (1964a)

g

VB-ETF

SCF-Min.STF SOC-MO

Best open-shell ETF

NO Expansion of Kolos -Roothaan Function

oc-soc

SOC-DODS ETF

SOC-ETF

SOC-ETF

SOC-ETF

Non-adiabatic 4 particle calculation

Accurate adiabatic calculation

Accurate non-adiabatic calculation

SOC ETF

SOC ETF

Vib-rot </ 1.92 -0.7175

T,w V 1.402 -1.15919

NO j/ Energy for truncated expansions

1.4 -1.16042

1.4 -1.16862

NO 1.4 -1.173128

2.3 -0.74371

Repulsive curve

D = 36091 cm"

1 R = 1.41913

o o „ „calc „exp . -1 H„ D =D r +4.2cm

2 e e

D calc = DexP +

-1

2 o o _calc „exp -1 D.D = D

v + 1.3 cm

2 o o w,Q,q • 1.947 -0.714533

uu,Q,q •" 1.96 -0.733439

Reference Description of Method E(R)

Browne (1964b)

Goodisman (1964)

SOC ETF

2^ , 2p

3n , 3d

XA , 3d3A xV

Gerhauser and Taylor (1964) ET

Wakefield and Davidson(1965) 2s £+

3s

3d

Wright and Davidson (1965) 3d n

Kolos and Wolniewicz (1965) XT

g

James-Coolidge trial function

SOC ETF

SOC ETF

SOC ETF A doubling

SOC ETF

Generalized James-Coolidge trial function

w.Q.q y 1.99 -0.757014

NO

w,Q,q \/ 1.99 -0.657178

Long range repulsive curve

-1.1738 • 1." -0.71643

<S 1.87 -0.72730

Vib-rot \S 1.864 -0.736615 y 1.990 -0.66048 s 1.984 -0.659325

Vib-rot \S 2 . -0.65929

Powers of i y 1.401 -1.1744746

E for large R Repulsive curve

Das and Wahl (1966)

Hoy land (1966b)

Extend. H.F. NO

OC STF

•s 1.951 -0.7183492 s 1.4 -1.169837 s 1.948 -0.73567 s 1.940 -0.71609

1/ 1.990 -0.65817

l/ 1.990 -0.65803
Reference State Description of Method E(R)

Rothenberg

(1966a) and Davidson 2P

1nu

3p

4f

4p

SOC ETF

Rothenberg

(1966b) and Davidson 2s L

g 3d

3s

2s

3I+

g 3d

3s2pVf

SOC ETF

3p

2p j. u 3p

2P

1

!! u 3p

4f

4p

2 P

3n

Vib-rot <S 1.950 -0.717961

Vib-rot \S 1.981 -0.655055

Vib-rot •s 2.000 -0.633939

Vib-rot </ 1.985 -0.632404

UJ,NO </ 2.00 -0.717244

'JJ,NO </ 2.00 -0.659817

UJ,NO s 2.00 -0.654481

W,N0 • 2.00 -0.735976

id, NO • 2.00 -0.660093

'J', NO \S 2.00 -0.659404

l/ 2.00 -0.750402

UJ,N0 \S 2.00 -0.664715 • Repulsive curve

D,NO f 2.00 -0.682866

id, NO v^ 2.00 -0.717832

id,NO v^ 2.00 -0.655035

'J), NO V 2.00 -0.633939

uu,NO w' 2.00 -0.632391

id, NO •* 2.00 -0.736849

Reference State Description of Method E(R)

Wolniewicz (1966)

3p

3n

4p

4f

xV

Kolos and Wolniewicz (1966a) B Lu

Kolos and Wolniewicz (1966b) XT

g

Hayes (1967) xV"

Num. integration nuclear motion

Generalized James -Coolidge trial Function

H-D perturbation correction to vibronic

function

ID, NO V* 2.00 -0.660233

ID, NO \S 2.00 -0.634470

ID, NO \/ 2.00 -0.633940

id, NO \S 2.00 -0.659284

ID, NO \S 2.00 -0.659362

id, NO y/ 2.00 -0.657444

id, NO (/ 2.00 -0.657502

H, D

Ca

2 o 1c _ DeXp + 3..9 cm 1

HD D"o lc _ DeXp + 4

o

,7 cm 1

1c _ DeXp + 3 .6 cm

•1

D to 1.6 cm"

1 2.43 -0.7566611

e

HD D C3lc

= DeXp + 1.9 cm"

1 o o

id,Q v^ 1.4 -1.17258
Reference Description of Method Basis Set E(R)

Anex (1963)

Michels and Harris (1963)

Conroy (1964b)

Preuss (1964)

Stuart and Matsen (1964)

Goodisman (1965)

Peyerimhoff (1965)

Wolniewicz (1965)

Gallup and McKnight (1966)

Harris (1966)

Hoyland (1966a)

X

1 ^

x

1 ^

xi^

xiZ+

X

l L+

x

1 ^

a

1^

x

1 ^

x

1 ^

X

1 ^

soc ETF

soc ETF

Minimize energy

variance

VB STF

OC-SOC Extend. STF

Generalized

James-Cool idge

SCF Hartree-Fock Extend. STF

Generalized

James-Cool idge

SCF

SOC

SOC

Exact 1-electron

diatomic

Non- integral ETF

S 1.40 -2.97424 s 1.40 -2.94321

*s 1.40 -2.977531 ^ 1.442 -2.94920

w- 1.40 -2.9691

-2.9729

1 ,40 -2 .93259

1 .4363 -2. 978669

Repulsive curve

1 .40 -2,.903

1.40

-2.9550

-2.97190

Reference Description of Method Basis Set E(R)

Michels (1966)

Michels and Harris (1963)

Taylor and Harris (1964)

Bender and Davidson (1966)

X

1 ^ SOC

A

1 ^ SOC bV

aV"

b

3^

cHi

c 3 n

X

2^ SOC

?_

ii SOC

?

; +

SOC x¥ soc xV SOC-NO

HeH

ETF

BTF

DODS-ETF

DODS-ETF

DODS-ETF

DODS-ETF

ETF U.Q

•" 1.40 -2.94321 w^ 6.0 -2.50124

1^" 8.5 -2.18177 \S 4.5 -2.50300

I** 8 . -2.20072 v" 8.0 -2.13318 v^ 8.0 -2.13761 • 3.0 -3.35670 Repulsive curve

v^' 1.5 -3.06983 • 1.5 -3.08304

3.0 -3.3618

3.0 -3.38280 Repulsive curve
Reference Description of Method Basis Set E(R)

Platas et al (1959)

Browne (1964c)

Cade and Huo (1967)

xV VB DODS STF /

Extend. STF+ETF

I 3.01 -7.699

VB I ^ 4.25 -7.7808

SCF Hartree Fock Extend. STF 3.014 -7.72943

LiH

Karo and Olsen (1959)

Robinson et al (1960)

Browne and Matsen (1962)

Ebbing (1962)

Fraga and Ransil (1962b)

Kahalas and Nesbet (1963)

Browne and Matsen (1964)

Csizmadia et al (1964)

xY VB Num. H.F. |1,ID V 3.245 -7.9941 aY V 4.90 -7.8963 xY VB DODS STF M 3.01 -8.0074 xY VB Extend. STF H,tt) y 3.075 -8.04379

SOC ETF M Y 3.0 -8.04127

SCF SOC Min. STF V 3.015 -7.9836

SCF SOC Extend. STF V-,1 y 3.0581 -8.0171

VB Extend. STF+ETF v,1,<» V 3.046 -8.0561 xY Group orbital SOC Hartree Fock AO V 3.0 -7.9922 aY y 3.0 -7.8773 Y y Repulsive curve

Reference State Description of Method Basis Set E(R)

Harris and Taylor (1964)

Ebbing and Henderson (1965)

Bender and Davidson (1966)

Csizmadia (1966)

Cade and Huo (1967a)

Sanders and Krauss (1967)

Kapral (1967) Michels (1967)

Cade and Huo (1967a)

X

1 ^ SOC

Gemina

1

SOC-NO

SCF

SCF Hartree-Fock

SOC-PNO Valence

SOC-MO-IS

x!£+ VB V VB

BeH+ xV SCF Hartree-Fock

DODS-ETF

ETF-N0

ETF

Extend. GTF

Extend. STF

Extend. GTF

GTF lobe

Min. STF + 2p

Min. STF + 2p

Extend. STF

y 3.2 -8.0387

3.0 -8.0179

n,q,Q 3.0147 -8.0606

H, ID V 3.02 -7.9842

ID, I <S 3.015 -7.98731

\S 3.0 -8.0188

\S 3.25 -7.9944 y 3.25 -7.9813 y Repulsive curve

2.479 -14.85396

Cade and Huo (1967)

LMSS (1967) XV

a\

BeH

SCF Hartree-Fock

SCF Hartree-Fock

Extend. STF

Extend. STF

W, I y 2.538

2.519

-15.15312

-15.05062

10
Reference

2.5 State Description of Method Basis Set E(R)

Cade and Huo (1967a)

LMSS (1967)

BH+

X^X+ SCF Hartree

ATL. SCF Hartree-Fock

Extend. STF

Extend. STF

2.296 -24.82064

2.374 -24.68317

Fraga and Ransil (1962b) Buenker et al (1967)

Cade and Huo (1967a)

Kaufman and Burnelle (1967) Harrison (1967)

xV

xV

3-,-

SCF-SOC Min. STF 2.329 -25.0903

SCF Extend. GTF lobe • -25.1001

SCF Hartree-Fock Extend. STF 11 . I w^ 2.305 -25.13147

SCF Extend. GTF 2.336 -25.1298

VB Valence GTF lobe AO n,Q,q ^ 2.50 -25.1455

n,Q,q v' 2.25 -25.1134

u,Q,q • 2.50 -25.0394

M,Q,q •* 2.50 -24.9948

H;Q,q V 2.25 -24.9207

Reference Description of Method Basis Set E(R) R

Moore et al (1965) X^+ VB Extend. STF

Cade and Huo (1967a) SCF Hartree-Fock Extend. STF

v^ 2.2356 -37.91786 V" 2.137 -37.90881

Cade and Huo (1967a) X

z

tl

CS

SCF Hartree-Fock Extend. STF i . I • 2.086 -38.27958

Cade (1967b) SCF Hartree-Fock Extend. STF 2.086 -38.29003
State Description of Method Basis Set E(R)

Cade and Huo (1967a) ^„

NH+

SCF Hartree-Fock Extend. STF 2.048 -54.50701

Joshi (1965)

Cade and Huo (1967a)

LMSS (1967)

Harrison (1967)

xY OC-SCF Extend. SXF H ^ 1.90 -54.9064

X

3!" SCF Hartree-Fock Extend. STF 111, I V 1.923 -54.97838 h SCF Hartree-Fock 1.9729 -54.91081 xV VBValence GTF lobe AO H ^ 2.375 -54.9400 h V- \S 2.375 -54.8625 Y H v- 2.375 -54.8312

3 n H sS~ 2.375 -54.7860

Reference State Description of Method Basis Set E(R)

Cade (1967b) X^Il SCF Hartree-Fock Extend. STF 1.923 -54.92138

Cade and Huo (1967a) xV SCF Hartree-Fock Extend. STF 1.944 -75.00050

0H

Cade and Huo (1967a) -X SCF Hartree-Fock Extend. STF

LMSS (1967) aY" SCF Hartree-Fock Extend. STF

UU,I •y 1.795

1.912

-75.42127

-75.26553

12
Description of Method Basis Set E(R)

Krauss and Ransil (1960)

Grahn (1964)

Rosenfeld (1964)

Moskowitz et al (1965)

Cade (1967a)

Fink et al (1967)

Ritchie and King (1967b)

x^+SCF

VB

SCF

SCF

Min. STF

Min. STF

Min. STF

Extend. GTF

v" 1.8342

1.8103

1.8103

1.8

-74.8785

-74.802

-74.8221

-75.3670

SCF Hartree'Fock Extend. STF H, Q, ui, q,EA ^ 1.781 -75.41754

SCF Extend. GTF lobe 1.85 -75.3413

SCI Extend. GTF 1.79 -75.3961

HF+

Clementi (1962a) v- SCF Extend. STF

Cade and Huo (1967a) x

2 n

± SCF Hartree-Fock Extend. STF

LMSS (1967) h

+ SCF Extend. STF

V' 2.5 -99.3988

1.7328 -99.53598

1.7328 -99.39246

Reference Description of Method Basis Set E(R)

Clementi (1962;

Nesbet (1962)

Bishop et al (1963)

Peyerimhoff (1963)

Harrison (1964)

Moccia (1964)

Moskowitz et al (1966)

Bender and Davidson (1967a)

Cade and Huo (1967a)

Erdahl et al (1967)

Whitten and Allen (1967)

McLean and Yoshimine (1967)

Harris and Michels (1967)

xV

HF

SCF

SCF

OC-VB (1)

VB (3)

SCF

OC-SCF

SCF

SOC-NO

SCF Hartree-Fock

VB

SCF

SCF Hartree-Fock

VB - Valence

Extend. STF M,* v/ 1.7328 -100.0580

Extend. STF H,T,w,f V" 1.7328 -100.0571

Non-integral n STF ^ 1.7052 -99.6651

Min. STF + 3d V 1.7328 -99.6271

Extend. GTF 1.75 -100.0178

Extend. STF M 1.7328 -100.0053

Extend. GTF v-,Q, q 1.7328 -100.0622

ETF i-i>Q.q 1.7328 -100.2577

Extend. STF n,Q,q,

iu,Q,q W 1.696 -100.07077

Extend. GTF lobe -100.1043

Extend. GTF lobe \i • -100.0224

Extend. STF M.Q.q.P 1.7328 -100.07046

Min. and DZ STF v^ 2.0 -100.0031

13
State Description of Method Basis Set E(R) R

Peyerimhoff (1965)

Fink et al (1967)

x

1^ SCF Hartree-Fock

SCF

Extend. STF

Extend. GTF lobe

U,UJ •- 1.83

1.93

-128.62836

-128.56239

HaH"*" Cade and Huo (1967b) 7TE+ SCF Hartree-Fock Extend. STF 3.566 -162.1671

Cade and Huo (1967b)

NaH xV" SCF Hartree-Fock Extend. STF uj,i ^ 3.566 -162.3928

Reference State Description of Method Basis Set E(R) R

Cade and Huo (1967b)

MgH"

X

L£+ SCF Hartree-Fock Extend. 3.116 -199.9082

MgH

Cade and Huo (1967b) xV" SCF Hartree-Fock Extend. STF

LMSS (1967) A

2n SCF Hartree-Fock Extend. STF

U),I */" 3.271 -200.1566

3.173 -200.0589

C3de and Huo (1967b)

LMSS (1967) A

2 n_

A1HT

SCF Hartree-Fock

SCF Hartree-Fock

Extend. STF

Extend. STF

3.027 -242.1930

3.007 -242.0542

14
Reference State Description of Method Basis Set E(R) R

Cade and Huo (1967b) ^

+

A1H

SCF Hartree-Fock Extend. STF «j, I v^ 3.114 -242.4634

Cade and Huo (1967b) xf SCF Hartree-Fock Extend. STF 2.874 -289.1656

Cade and Huo (1967b) X

zn SCF Hartree-Fock Extend. STF it, I v/ 2.874 -289.4362

Reference State Description of Method Basis Set P E(R) R

Cade (1967b) X

3^" SCF Hartree-Fock Extend. STF 2.861 -289.4598

Cade and Huo (1967b)

FH+

SCF Hartree-Fock Extend. STF 2.693 -340.9386

Cade and Huo (1967b)

LMSS (1967) xY

i.

PH

SCF Hartree-Fock

SCF Hartree-Fock

Extend. STF uu,I v^ 2.708 -341.2932

Extend. STF 2.708 -341.2473
Reference State Description of Method Basis Set E(R) R

Cade (1967b)

PH" X n SCF Hartree-Fock EA -3A1.2847

Cade and Huo (1967b)

SH SCF Hartree-Fock Extend. STF '.551 -397.7593

LMSS (1967) Cade and Huo (1967b)A

2^

A.

SH

SCF Hartree-Fock

SCF Hartree-Fock

Extend. STF 2.551 -397.9441

Extend. STF u),I y/ 2.551 -398.1015

Reference State Description of Method Basis Set E(R) R

Cade (1967a) XT; SCF Hartree-Fock Extend. STF H,Q,u>, V' 2.551 -398.1459

q,EA

HC1+

Cade and Huo (1967b) x

2 n

i SCF Hartree-Fock Extend. STF

LMSS (1967) A

22+ SCF Hartree-Fock Extend. STF

2.485 -459.6752

2.861 -459.5376

16
Reference State Description of Method Basis Set E(R)

HC1

Moccla (1962)

Nesbet (1964b)

Cade and Huo (1967b)

McLean and Yoshimine(1967)

KV OC-SCF Extend. STF H

SCF Extend. STF

i',T SCF Hartree-Fock Extend. STF W,I

SCF Hartree-Fock Extend. STF KQ,

2.404 -458.83776 ^ 2.4085 -459.80374 V 2.4087 -460.1103

2.4087 -460.11185

Reference Description of Method Basis Set E(R)

Kolos and Roothaan (1960)

Fraga and Ransil (1962 a)

McLean et al (1962)

Conroy and Bruner (1966)

Michels (1967)

g h

+

g V

^

+

u

(2)lj,+*

40-tertn James-Coolidge

Junction

S0C-SCF-M0 Extend. STF

SOC Extend. STF

Minimize energy variance

VB Extend. STF

• 1.3 -3.67964

V-" 1 . 3 -3.66562 *r 1.3 -3.66222

(•" 1.375 -3.6793 b ^

, 1.5 -3.6519

v" " Repul sive curves V 3. 'J -2.3922 V Repul sive curves

Reagan et al (1963)

Conroy and Bruner (1966)

Edmiston and Krauss (1966)

Gilbert and Wahl (1967a)

Browne (1966)

u

^u

4*,<2s„V

He

2 VB Extend. STF

Minimize energy variance

S0C-PN0 Extend. GTF

SCF Hartree-Fock Extend. STF

VB STF-ETF

2.00 -4.98540

2.00 -4.9846

2.0626 -4.9841

Curve relative to calculated asymptote

6.0 -4.21497

Repulsive curves

Reference State Description of Method Basis Sat E(R)

Michels (1967)

Schwartz (1967)

He,

xV" VB

u

g

(4)V*,^ (3)^^.V

xV

Extend STF

SCF Hartree Fock Floating S GTF

2.05 -4.97068

1.5 -4.0451

1.5 -3.83927

1.5 -4.07516

Repulsive curves

2.06 -4.92109

17
Reference Description of Method Basis Set E(R)

He

Moore (1960)

Ransil (1961)

Phillipson (1962)

Kim (1962)

Miller and Present (1963)

Kestner (1966)

Kestner and Sinanoglu (1966)

Barnett (1967)

Gilbert and Wahl (1967b)

Matsumoto et al (1967)

Morris and Present (1967)

Brigman et al (1961)

Poshusta and Matsen (1963)

Scott et al (1966)

8 VB Extend. STF %/ Repulsive curve

SCF Extend. STF >S for the ground state

SOC-MO Extend. STF V

VB Extend. STF E at large R

OC Extend. STF E at large R

Pair Corre lat ion6 E at large R

Pair Corre lations E at large R

SOC ETF-DODS V

SCF Hartre e-Fock Extend. STF s

S0C-N0 ETF E at small R

OC-SOC Extend. STF E at small R V VB STF-DODS Pot. ,/ 2.13 -5.0938

u hump V VB Extend. STF Pot. >/ 2.13 -5.11346

u hump

UU,Q ^ Extend. STF v^ -5.10509

Reference State Description of Method Basis Set E(R)

Li

LMSS (1967) X^"1" SCF Hartree-Fock Extend. STF

8 2„

Tl SCF Hartree-Fock Extend. STF

5.051 -14.70971

5.051 -14.54197

Li„

Fraga and Ransil (1962b)

Das and Wahl (1966)

Das (1967)

Buenker et al (1967)

Cade and Wahl (1967)

Kapral (1967)

rilr.+ SOC Min. STF 5.051 -14.8523

Extend. H. F. -Valence Extend. STF UJ »/ 5.25 -14.8988

Extend. H.F. -Valence Extend. STF (U • 5.07 -14.90260

SCF Extend. GTF lobe -14.86501

SCF Hartree-Fock Extend. STF It) \S 5.37 -14.87179.

SOC-MO-IS GTF lobe A0 ID \S 5.5 -14.88715

18
Description of Method Basis Set E(R) 3£5

Fraga and Ransil (1962b) X^"1

"

LMSS (1967)

Bender and Davidson (1967c) XT

g Vu

3"g

SCF Hartree-Fock Extend. STF

SOC NO; r MO

SOC Extend. ETF

3.78 -29.10537

Repulsive 8.50 -29.14667 curve Repulsive 4.5 -29.21998

curve • 4.5 -29.14586 • 4.0 -29.11909 V 4.0 -29.10969

Padgett and Griffing (1959) X

3£"

u Bender and Davidson (1967b) X

5£~

'Ilu

LMSS (1967)

SCF

SOC

SCF Hartree-Fock

Mln. STF

Extend. ETF

Extend. STF

T <S 3.0769 -49.063

T v" 3.U0 -49.1453 V" 3.00 -49.1402. ^ 3.00 -49.1144

Q,q 3.005 -49.09087

Reference Description of Method Basis Set E(R)

Fraga and Ransil (1962b) < 1E+

g SOC Min. STF

Fougere and Nesbet (1966)

g x\

SOC

SOC

DZ+3d UU,T

Buenker et al (1967) xls+ SCF Extend. GTF lobe

Verhaegen et al (1967)

g SCF Extend. STF <.T ^

LMSS (1967)

g SCF Hartree--Fock Extend. STF Q,q

A

3!; SCF Hartree--Fock Extend. STF Q-q

2.3475 -75.3193

Curves relative to calculated asymptote.

-75.3500.

2.3716 -75.385

2.3481 -75.40620

2.5876 -75.51523

19
Description of Method Basis Set E(R)

Cade et al (1966)

Verhaegen et al (1967b)

2 8 SCF Hartree-Fock Extend. STP

SCF Hartree-Fock Extend. STF bVu SCF Hartree-Fock Extend. STF ** SCF Nesbet Extend. STF

A2n SCF Nesbet Extend. STF

V^ 2.0385 -108.4079

<S 2.134 -108.4320 • 1.934 -108.2702 y 2.068 -108.3645 v/ 2.068 -108.3877

Richardson (1961)

Fraga and Ransil (1962)

Nesbet (1964) Nesbet (1965) Cade et al (1966)

Buenker et al (1967)

Kapral (1967)

X

lr+ SCF DZ T 2.067 -108.7853

g SOC Min. STF 2.086 -108.6605 xV SCF Extend. STF Q,U) <S 2.068 -108.9714

g MO-Excited states Extend. STF T,uu

s x^

SCF Hartree-Fock Extend. STF U) \/ 2.0132 -108.9956

SCF Extend. GTF lobe -108.9189

Xljr1- S0C-M0-IS GTF lobe AO U) y/ 2.24 -108.9441

Reference Description of Method Basis Set E(R)

LMSS (1967-) SCF - Hartree-Fock Extend. STF 2.122 -149.2257

Sahni and DeLorenzo(1965)

LMSS (1967)'

g SCF Min. STF yh\ SCF -> Hartree-Fock Extend. STF °\ SCF -• Hartree-Fock Extend. STF

g SCF - Hartree-Fock Extend. STF

2.28167 -149.0921

Q,q %/ 2.282 -149.6659

\/ 2.297 -149.6172 • 2.318 -149.5683

20
Reference State Description of Method Basis Set E(R)

LMSS (1967) x

2n SCF - Hartree-Fock Extend. STF >s 2.40 -149.6427

LMSS (1967) X

z

fl SCF

SCF

SCF

SCF

1

Extend. STF

Extend. STF

Extend. STF

Extend. STF

2.525 -198.1782

2.525 -197.9972

2.525 -198.0559

2.525 -197.3507

Reference Description of Method Basis Set E(R)

Hijikata (1961)

Fraga and Ranail (1962b)

Wahl (1964)

Das and Wahl (1966)

Buenker et al (1967)

LMSS (1967)

Kapral (1967)

Das and Wahl (1967)

Horsley and Richards (1967)

Harris and Michels (1967)

g VB Min . STF T S 2.664 -197.9437

xl£+

g

see Min. STF 2.680 -197.9558

Xl£+

g SCF Hartree-Fock Extend. STF w,Q,q

T 2.680 -198.7683

I«J* Extend. H.F. Valence Extend. STF v' 3.0 -198.8378

xir+

g

SCF Extend. GTF lobe -198.6929 x^ SCF Hartree-Fock Extend. STF Q.q 2.525 -198.7761

x

1^g SOC-MO-IS GTF lobe AO Ul <y 3.25 -198.7754

xir^

g Extend. H.F. -Valence Extend. STF v/ 2.68 -198.8546

xi£+

g SCF Extend. STF U),T • 2.68 -198.7814

3n SCF-Nesbet Extend. STF III >s 2.98 -198.6792 K V Repulsive curve X •" Repulsive curve

x

1^g VB DZ STF v^ 3.1 -198.8179

Gilbert and Wahl (1967a) 2r+ xt: SCF Hartree-Fock Extend. STF i-'.T v*1" Curve relative to calculated asymptote

21
State Description of Method Basis Set E(R) R

Ne"7

.2 _+ Gilbert and Wahl (1967a) X £ SCF Hartree Fock Extend. STF *S Curve relative to calculated asymptote

Gilbert and Wahl (1967b) X^"*" SCF Hartree Fock Extend. STF y/ Repulsive curve

State Description of Method Basis Set E(R) R

Ransil (1964) X

1!"1" g LMSS (1967) X

1^

Bertoncini and Wahl (1967) X

1!?

SCF

SCF

SCF

Min. STF

Extend. STF

Extend. STF

w V* 5.8178 -322.3775

Q,q 5.8178 -323.7116

Q \Z" 5.8 -323.7096

Ransil (1964)

lL+

SCF

Mg„

Min. STF 6.1 -397.8652

Ransil (1964) 3E~ SCF

g h

g

Al.

Min. STF 4.838 -482 .3287

4.833 -482 ,3237

4.838 -482 .3003

Ransil (1964) \~ SCF

g X

hi

\S 4.5 •S 4.653 V^ 4.653

-576.2190

-576.1893

-576.1645

22
Reference State Description of Method Basis Set E(R) R

Ransil (1964)

Boyd and Lipscomb (1967)

lE+ SCF Min. STF

g SCF Min. STF+3d W 3.5798

3.850

-679.8020

-679.1664

Ransil (1964)

g SCF

s„ v 3.93 -793.2791

\S 3.57 -793.2393 V 3.57 -793.2055

LMSS (1967

C1+

x

2n SCF Extend. STF \ SCF Extend. STF

2r SCF Extend. STF

3.5748 -918 .5171

4.25 -918 .4230

3.7564 -918 .3938

Ransil (1964)

Gilbert and Wahl (1967c)

xlE+ SCF

g X

1^ SCF

g

CI*

Min. STF

Extend. STF

4.1

3.8

-917.0723

-918.9871

Reference State Description of Method Basis Set E(R) R

Gilbert and Wahl (1967a) ^ SCF Extend. STF p T j/ Curve relative to computed asymptote

Gilbert and Wahl (1967a) xV' SCF

Ax,

Extend. STF u-.T \S Curve relative to computed asymptote

Gilbert and Wahl (1967b) X^"1" SCF

g

Ar„

Extend. STF y/ Repulsive curve

23
State Description of Method Basis Set E(R) R

Schneiderman and Michels

(1965) zV

+

HeLi SOC-DODS ETF y 4.0 -10.1272

Scheel and Griffing (1962) X

2t

Schneiderman and Michels

(1965)

a

2 h

a4n

HeLi

2 S

+ 2£*** , 2j;****

Min. STF ^ Repulsive curve

T s Repulsive curve

U) \S 3.5 -10.2550

111 • 6.0 - 9.617

(U • 6.0 - 9.6322

HI 1/ 5.0 - 9.5992 v^ Repulsive curves «/

Allen et al (1966) V* Extend. GTF lobe v/ Repulsive curve

State Description of Method Basis Set E(R) R

Allen et al (1966)

Michels (1967) %+' n vb

2 E+*

HeNe"r Extend. GTF lobe

Min. STF

*>/ Repulsive curve

V' Repulsive curves S 4.0 -129.81825

Matcha and Nesbet (1967) xV" SCF Hartree-Fock BA+P STF s/ Repulsive curve

Matcha and Nesbet (1967) sy

HeAr

SCF Hartree-Fock BA-H> STF v^ Repulsive curve

24
Reference Description of Method Basis Set E<R)

LMSS (1967) ijT*" SCF - Hartree-Fock Extend. STF , Q, q S 4.60 -31.95508

LMSS (1967) II SCF - Hartree-Fock Extend. STF U, Q,q v" 3.80 -45.11185

LMSS (1967)

3 -

LiN

£ SCF -• Hartree-Fock Extend. STF \l, Q, q \S 3.40 -61.82640

Description of Method Basis Set P E(R) R

LMSS (1967) SCF GTF lobe AO 3.184 -81.88621

LMSS (1967)

LiO

II SCF - Hartree-Fock

SCF - Hartree-Fock

Extend. STF

Extend. STF

U, Q, q V 3.184

3.184

-82.31113

-82.29619

Fraga and Ransil (1962b) xh+

McLean (1963b)

McLean (1964)

McLean and Yoshimine(1967)

LMSS (1967) Xl£+

Pfeiffer (1967) X^+ ^

LiF

SCF-SOC Min. STF

SCF BA+P STF

SCF-Scale optimization Extend. STF

SCF- Hartree-Fock BA+P STF

SCF - Hartree-Fock Extend. STF

VB GTF lobe AO

Wahl et al (1967) :fr SCF BI STF2.85 -106.41211

H,Q • 2.8877 -106.98850

\j',m V 2.89 -106.97690

li.Q.q.Pv/ 2.8877 -106.9916

H, Q,q 2.955 -106.9904

H,q 3.000 -106.9534

3.000 -106.7177

\i. 2.955 -106.97®

25
State Description of Method Basis Set E(R)

LMSS (1967)

LMSS (1967) 2j;+ SCF

GTF lobe AO

GIF lobe AO

2.955 -106.6364

2.955 -106.6175

LMSS (1967)

Bertoncirti and Wahl

(1967)

Matcha (1967)

LMSS (1967)

Wahl et al (1967)

LiHa zh+ SCF Extend. STF

x

1^ Extend. H.F. -Valence Extend. STF

SCF Hartree-Fock Extend. STF

Li CI

1z+ SCF Hartree-Fock BA+STF xV SCF Extend. STF

x

1^ SCF BI STF

H,Q,q 5.30 -169.2880

<» "S 5.50 -169.31422 w V 5.50 -169.2919

U),|i,q V 3.825 -467.05466 Q

H,Q,q 3.81855 -467.0499

4.71 -467.0116

Reference State Description of Method Basis Set E(R) R

Matcha (1967) Extend. STF v-,1 v 4.0655 -2579.8901

LMSS (1967) SCF

SCF

Extend. STF 2.5149 -89.15694

2.5149 -89.11320

26
Description of Method Basis Set E(R)

Yoshimine (1964) X E

Verhaegan and Richards (1966) X Z

McLean and Yoshimine (1967) X Z+

Huo et al (1967) X S+

a

3n A

1

!,

BeO

SCF Hartree-Fock

SCF MO-SOC

SCF Hartree-Fock

SCF Hartree-Fock

SCF Hartree-Fock

SCF Hartree-Fock

Extend. STF H,uj, Q y 2.4377 -89.44787

Extend. STF T y 2.676 -89.4282

BA-t¥ V,Q, q y 2.4377 -89.4541

Extend. STF H, x y 2.5149 -89.4499

Extend. STF p., uu y 2.7647 -89.4877

Extend. STF |JL, IU v' 2.7647 -89.4835

LMSS (1967) Extend. STF -113.8388

EeF

LMSS (1967)

Walker and Richards (1967)

x

2z+

SCF Extend. STF X SCF X SCF

X

2E+

SCF Nesbet Hartree-Fock Extend. SXF X SCF Nesbet

2n SCF Nesbet

M,Q,q 2 .572 -114.1688

2..634 -113.8904

2,,634 -113.9982

2,.572 -114.1859

2 .57 2 -113.9164

2,.572 -114.0163

1*.+ Bender and Davidson (1967a) X Z DZ-STF 3.0 -143.038

Reference Description of Method Basis Set E(R)

Verhaegan and Richards (1967) X

1^

LMSS (1967)

LMSS (1967)

3 +

Z

HI-ii i

BeS

SCF Extend. STF

BM SCF

SCF

Extend. STF

Extend. STF

• 3. 1 -412.0971

5. 1 -412.0835

3.3 -412.0729

3.3 -412.0287

2.421 -78.54305

2.421 -78.49302

Verhaegen et al (1967)

LMSS (1967)

lr+

BN

SCF Nesbet

SCF

Extend. STF uu T y 2.30 -78.90 04

Extend. STF

q 2.421 -78.96701

27
State Description of Method Basis Set E(R)

LMSS (1967)

SCF

Extend. STF 2.275

2.275

-99.06898

-98.97693

BO

LMSS (1967) x

2^

2n

i

2n

SCF

SCF

SCF

Extend. STF

q 2.275 -99.55550

Extend. STF

q 2.555 -99.47757

Extend. STF

q 2.275 -99.24030

LMSS (1967) SCF Extend. STF 2.275 -99.59493

Reference State Description of Method Basis Set E(R) R

LMSS (1967) h+ SCF \ SCF h SCF

Extend. STF

Extend. STF

Extend. STF

2.391 -123. 7952

2.64 -123. 5769

2.391 -123. 5499

Fraga and Ransil (1962)

Nesbet (1964)

Huo (1965)

Lefebvre-Brion and Moser

(1965)

McLean and Yoshimine(1967)

Kapral (1967)

Xl£+

X

lZ+

BF

SOC

SCF

SCF Hartree-Fock

Min. STF

Extend. STF

Extend. STF

Excited M0 Extend. STF

X

1^ SCF Hartree-Fock BA-H? x4:+ SOC -MO-IS GTF lobe AO

yi 2.385 -123.6756

U,Q,«> V'

v'

2.385 -124.14038

2.354 -124.1664

H.Q.q.Pv' 2 - 391 -124.1671

uu V 2.5775 -124.0962

28
State Description of Method Basis Set E(R)

LMSS (1967) V

Extend. STF 2.217

2.576

-91.6410

-91.75452

LMSS (1967) h SCF

CN

Extend. STF 2.214 -91.85104

LMSS (1967) x%+ :;<:!' X SCF

2K SCF

CI i Extend. STF 2.107 -112.2915

2.350 -112.2304

2.107 -111.9131

State Description of Method Basis Set E(R)

CO

Lefebvre-Brion et al (1960) Excited MO

Merryman et al (1960) Excited MO

Lefebvre-Brion et al (1961) Excited MO

1 +

Fraga and Ransil (1962b) X £ SOC

Lefebvre-Brion et al (1964) Excited M0

1 +

Nesbet (1964) X £ SCF

Nesbet (1965)

Huo (1965)

Excited M0 xV

1 + McLean and Yoshimine (1967) X £

Huo (1966) a 3 n

SCF Hartree-Fock

SCF Hartree-Fock

SCF Hartree-Fock

Min. STF

Min. STF

Min. STF

Min. STF

Extend. STF

Extend. STF

Extend. STF

Extend. STF

Extend. STF

Extend. STF

T S

T •

T -y 2.1319 -112.5752

2.132 -112.3960

ID 2.132 -112.7588

T >S

q,lD 2.081 -112.7879 u,Q,q,P/ 2.132 -112.7891

p,Q,q • 2.2853 -112.5742

LMSS (1967)

CF

Extend. STF 2.322 -136.8862

29
Reference State Description of Method Basis Set P E(R) R

LMSS(1967) Extend. STF

q 2.402 -137.2169

Richards (1967) X

1 ^

CS

Extend. STF 2.89964 -435.3297

NO

Lefebvre-Brion and Moser(1966) Excited SCF-MO

LMSS (1967) X^"1" SCF

Extend. STF Extend. STF

Excitation energies only

2.007 -128.9560

State Description of Method Basis Set P E(R) R

Lefebvre-Brion and Moser

(1965) Excited SCF-MO Extend. STF Excitation energies

only

Lefebvre-Brion and Moser

(1966)

LMSS (1967)

Excited, Nn +

2 X IL

Extend. STF

Extend. STF U,Q,1

Excitation energies

only

2.1747 -129.2837

Reference State Description of Method Basis Set P E(R) R

Allen et al (1966) lv +

NeO

Extend. GTF lobe V" Repulsive cur

Allen et al (1966)

NeF

Extend. GTF lobe Repulsive curve

Matcha and Nesbet (1967) X

LZ+ SCF \S* Repulsive curve

30
State Description of Method Basis Set E(R) R

Matcha (1967)

Wahl et al (1967)

Das and Wahl (1967)

NaF V" SCF Hartree-Fock

SCF Hartree-Fock

Extend. Hartree-Fock

BA4P STF

BI+P STF

a>,\l,q y 3.628 -261.37849

Qw,P t/ 3,5 -261.3773

NO,

m

\/ 3.65 -261.4002

Matcha (1967) V

Wahl and Gilbert (1967)

NaCl

SCF Hartree-Fock

SCF Hartree-Fock

BA+P STF

BI+P STF

U),li,q \S 4.485 -621.4574

Q

ui,(ji, v^ 4.461 -621.4398

Born parameters

Matcha (1967) V

NaBr

Extend. STF IJ.q 4.729 -2734.2876

Reference State Description of Method Basis Set E(R) R

Richards et al (1966)

a J n

MgO

SCF

SCF Nesbet

Extend. STF

Extend. STF

McLean and Yoshimine (1967) E SCF Hartree-Fock Extend. STF (J.

, Q ,

q

V 3.4 V 3.4 V 3.3

w^ 3.3052

-274.2784

-274.3331

-274.4757

-274.3751

Walker and Richards (1967) V

MgF

SCF Nesbet Extend. STF v' 3.25 ^ 3.25-299.0790

-298.9493

McLean and Yoshimine (1967) 1£

+

A1F

SCF Hartree-Fock Extend. STF HfQ.q.P S 3.126 -341.4832

31
Reference State Description of Method Basis Set P E(R) R

SiO

McLean and Yoshimine(1967) lZ+ SCF Hartree-Fock Extend. STF u.Q.q.P \S 2.75 -363. 8523

McLean lr+ and Yoshimine(1967) 1£T

SCF Hartree-Fock Extend. STF H,Q,q,P V 2.67 -395.1857

Boyd and Lipscomb(1967) II SCF Min. STF-H'Sd 2.738 -414.1371

Reference State Description of Method Basis Set P E(R) R

3oyd and Lipscomb(1967) \' Min. STF+P3d 2.859 -414.116

Stevens (1967a)

1 +

t

C1F

SCF Hartree-Fock Extend. STF 3.0768 -558.8955

Matcha (1967)

Wahl et al (1967)

lv+

KF

SCF Hartree-Fock

SCF

H,q • 4.1035 -698.68501

M 4.9720 -698.6645

Matcha (1967)

KC1

Extend. STF H,q >y 5.039 -1058.7583

32
Reference State description of Method Basis Set P E(R) R

McLean and Yoshimine(1967) V"

CaO

SCF Hartree-Fock Extend. STF M-,q,q y 3.4412 -751.5591

Carlson et al (1965)

Sen

X^ST" SCF Extend. STF T,w,n., y 3.05 -888.178

Carlson and Moser(1967) ^E+

Cheetham and Richards (1967) IT

ScF

SCF

SCF Nesbet

Extend. STF

Extend. STF

T,uj,u v^ 3.31

T ^ 3.51

T •* 3.61

T S 3.71

T V 3.51

-858.5453

-858.5107

-858.4564

-853.4230

-858.4166

Reference State Description of Method Basis Set E(R) R

Carlson and Moser (1963)

Carlson and Nesbet (1964)

Carlson and Moser (1967)

u +

X-V,

SCF

SCF

MO

SCF

Min. STF+P

Extend. STF

Extend. STF

Extend. STF

T,u.,u) V 3.0618 -921.4959

H,U) V 3.0618 -921.5418

T,h.,uu • 2.91 -922.4976

Carlson and Moser (1966) vSCF

MO

Vii

Extend. STF

Extend. STF

2.91 -1015.7627

2.91 -1015.8917

33
State Description of Method Basis Set P E(R) R

Matcha (1967) V SCF Extend. STF n,q 4.3653 -3037.7727

McLean and Yoshimine(1967) lZ+ SCF H,Q,q,P • 3.6283 -3206.2311

State Description of Method Basis Set E(R)

Christoffersen et al (1964) LA

Conroy (1964a) lk

Conroy (1964b) *A

Christoffersen (1964) J-A

Hoyland (1964) lk

Lester and Krauss (1966) A

Pearson et al (1966) *A

Joshi (1966) 1A

Conroy and Bruner (1966) E Considine and Hayes (1967) '•A

Schwartz (1967) lA

Schwartz (1967) *A

SOC-VB

Minimize energy variance

Minimize energy variance

S0C-M0 Extend. STF

VB Generalized ETF

Correlated Closed-Shell Extend. GTF

VB Generalized GTF

OC-SCF Extend. STF

Minimize energy variance

0C-S0C Extend. STF

SCF - Hartree-Fock Floating S GTF

S0C-M0-"0ut of-plane" Floating S GTF

Correlation included.

Equilateral • 1.625 -1.30Q2

<y Energy surface wS 1.68 -1.357 • 1.6575 -1.3326

1.68 -1.2726

1.68 -1.2984

•• 1.66 -1.3185 v 1.6229 -1.2863

•S 3.0

Linear

-0.6721

1.8 -1.2466

1.6405 -1.2999

1.6504 -1.3376

34
Description of Method Basis Set E(R)

H

Boys and Shavitt (1959)

Hoyland (1964)

Krauss (1964)

Edmiston and Krauss (1965)

Conroy and Bruner (1965)

Conroy and Bruner (1966)

Considine and Hayes (1967)

Shavitt et al (1067)

Schwartz (1967)

Edmiston and Krauss (1967)

V Extend. STF

Generalized ETF

Extend. GIF

Extend. GIF

SOC-VB

SOC-VB

SCF - Hartree-Fock

SOC-PNO

Minimize energy variance

Minimize energy variance

OC-SOC Extend. STF

SOC Extend. STF

SCF - Hartree-Fock Floating s GTF

SOC-PNO Extend. GTF

u </ 1.778 -1.6274

1.78 -1.5889 V 1.73 -1.5930

1.3 -1.6493

K* Energy surface «" 1.75 -1.6551

1.8 -1.6121

Surface •* 1.8 -1.6521

1.7 -1.5940

Surface y/' 1 & -1.6493

Roberts (1963)

Krauss and Mies(1965)

lA VB Min. STF

1

lA SCF - Hartree-Fock Extend. GTF

1

LiHI

Preuss and Diercksen (1967) X

1!4" SCF

g Extend. GTF

E at large R V ^ Analytic interaction potential ^ 3.5 -8.5313

Reference State Description of Method Basis Set E(R)

Peyerimhoff et al (1966) SCF

Harris and Michels (1967) VB

Extend. GTF lobe

Min. STF S 2.54

i/ 2.54

-15.7123

•15.7202

Peyerimhoff et al (1966)

g Extend. GTF lobe v 2.45 -25.4363

Peyerimhoff et al (1966) *A

Geller et al (1967) XA

BH

2 SCF

SCF -Hartree-Fock

Extend. GTF lobe

Extend. GTF

2.35, 104°

.-25.6823

2.222, 131° -25.7086

35
Reference State Description of Method Basis Set E(R) R

Krauss (1964)

Foster and Boys (1960)

Harrison (1967)

V8

lA

SCF

SCF

SOC

SOC

SOC

VB

IB,

Extend. GTF v^ 2.1,105 -38.3026

Extend. GTF v^ 1.95 -38.8936

Min. STF+DZK 11) • 2.11,129° -38.904

Min. STF+DZK U) s/ 2.21,90° -38.865

Min. STF+DZK U) s 2.11,132° -38.808

Extend. GTF lobe x/ 2.0,138° -38.893 • 2.0,108° -38.843

<s 2.0,148° -38.822

Peyerimhoff et al (1966)

NH+

2 Extend. GTF lobe ^ 2.05,130 -55.0932

Reference State Description of Method Basis Set P E(R) R

Krauss (1964) 'B SCF

1 Extend. GTF v' 1.95,105 -55.4537

Fink et al (1967)

Ritchie and King(1967b)

L A SCF

1 SCF Hartree-Fock

GTF lobe AO

Extend. GTF

2.05,100 -55.3795

1-903, -55.5077

105

Krauss (1964)

Miller et al (1967)

2 B SCF

2B SCF

H2(T Extend. GTF Extend. GTF

V* 1.9,115 -75.4465

1.81,105° -75.6025

36
Description of Method Basis Set E(R)

McWeeny and Ohno (1960)

Krauss (1964)

Moccia (1964c)

Moskowitz and Harrison (1965)

Fink et al (1967)

Ritchie and King(1967a)

Snyder (1967)

Miller et al (1967)

Fink et al (1967)

H

2 \ Group Orbital Min. STF \ SCF Extend. GTF \ OC-SCF Extend. STF M

1Al SCF Extend. GTF M \ SCF Extend. GTF lobe AO M

SCF Extend. GTF

SCF Extend. GTF \ SCF Extend. GIF L> \ SCF Extend. GTF \ SCF

H

2 F+

Extend. GTF

\ SCF GIF lob e AO

V

/

1.8.105° -75.8453

1. 814. 106°-75. 9224

1.8.105" -76.0421

1.83.110* -76.0031

1.8,105" -76.0343

1.81098 -76.020

104°26'

1.81.105° -76.0161

1.81,105° -75.7788

1.81,105° -75.7642

1.9.130° -100.1773

Reference State Description of Method Basis Set E(R)

(H,F)

Ritchie and King (1966) r [ Extend. GTF •" 1.9,2.2 -100.575

Kapral (1967) 'V.' GTF lobe AO \S Repulsive curve

Moccia (1964c)

H2

S

OC-SCF Extend. STF 2.509,89 -397.5891

37
Reference State Description of Method Basis Set P E(R) R

Preuss and Diercksen (1967) L.t SCF Extend. GTF S 3.; -15.2387

Preuss and Diercksen (1967) 1£+ SCF

(Li 2H)

Ex tend. GTF w S 3.41 -15.3874

Reference State Description of Method Basis Set P E(R) R

Buenker and Peyerimhof

f

(1966)

Ritchie and King (1967b)

1 +

r

SCF Hartree-Fock

Extend. GTF lobe

Extend. GTF

<s 3.0236, 1.833 -82.9092

3.00, -82.9285

1.79

McLean (1962) ^

McLean and Yoshimine(1967) £

Pan and Allen (1967)

Buenker and Peyerimhoff

(1966)

V

HCN

SCF

SCF Hartree-Fock

SCF

FOH

Min. STF 2.0,2.18 7 -92.5474

BA+P V, Q. i> p 2.014, <S 2.179 -92.9147

Extend. GTF lobe A0 U,Q 2.00, 2.1775 -92.8287

Extend. GTF lobe • 2.65, -174.7196

1.833,

100°
Reference State Description of Method Basis Set E(R) R

dementi (1961)

Clementi and McLean

(1962b)

Erdahl (1967)

lp+

12+

(FHF) SCF

SCF

VB-Valence

Min. STF 2.135 -198.2826

Extend. STF 2.126 -199.3791

Extend. GTF lobe .i. *S 2.2 -199.4924

AO

McLean and Yoshimine

(1967) DZ+P STF Q,q,P V 2X -199.5730

Peyerimhoff et al (1967) V1

" Extend. GTF lobe 2.072 -213.6527

Buenker and Peyerimhoff (1966) 1E+ SCF Extend. GTF lobe •S 3.313 - 89.7743

Allen et al (1965) l A VB Extend. GTF lobe

Clementi (1961)

Clementi and McLean

(1962a)

!£+ SCF Min. STF

Extend. STF

2.519 -113.0875

2.519 -113.1652

Reference State Description of Method Basis Set P E(R) R

NeC

Ha and Allen (1967) \ GTF lobe AO \^ Repulsive curve

McLean and Yoshimine

(1967) lr+

(OCN)

SCF Hartree-Fock BA+P STF [i,Q,q,P 2.213,

2.281 -167. 26S

McLean and Yoshimine (1967) 1E+

McLean and Yoshimine (1967)

FCN

SCF Hartree-Fock

(SCN)"

BA+P STF U , Q,q,P 2.38109,

2.20156 -191. 77S

n,Q,q,P 2.95, 2.30

McLean and Yoshimine (1967) SCF DZ+P STF M,Q,q,P 3.0784, -551.8247 2.1978

39
Reference State Description of Method Basis Set E(R) R

McLean (1960) Xr8 SCF

McLean (1963)

g SCF

Peyerimhoff et al (1967) *K SCF

Min. STF

Extend. STF

Extend. GTF lobe AO

:Lean and Yoshiraine(1967) X

1^ SCF Hartree-Fock BA+P STF Q,q

2.1944 -136.8427

2.1944 -186.9300

2.196 -187.4929 • 2.1944 -187.7228

McLean and Yoshimine (1967) X

1!^ SCF ^.Q.q.P

2.9442, 2.2016 -510.3309

Clementi (1961) £

g Cletnenti and McLean

(1963) ^

Peyerimhoff and Buenker (1967) L

SCF

SCF

Extend. STF

Extend. GTF lobe T

2.217 -162.5422

2.268 -162.7048

2.20 -163.1123

McLean and Yoshimine (1967) U

N

2

H.Q.q.P 2.1273, 2.2418 -183.7567

Ha and Allen (1967) GTF lobe AO \S Repulsive curve

Reference State Description of Method Basis Set E(R) R

no; Clementi (1961) 1~+

Clementi and McLean

(1963) hi*

g SCF

Pfeiffer(1967) X SCi

Min. STF

Extend. STF

Extend. GTF lobe

2.173 -202.9011

2.173 -203.1082

2.1806 -203.4547

Pfeiffer (1967) lA SCF

1 DZ GTF lobe AO 2.3356, -203.9551 115.4

Geller et al (1967) \ GTF V 2.58, -250.0189

103°

40
Reference State Description of Method Basis Set E(R) R

Peyerimhoff and Buenker(1967) X A SCF GTF lobe AO 2.50 „ 116.8 -224.1618

Ha and Allen (1967) 'A SCF GTF lobe AO v^ Repulsive curve

Buenker and Peyerimhoff

(1966) l A SCF

1

F,n

Extend. GTF lobe 2.64, 102° -273.4456

Reference State Description of Method Basis Set E(R) R B72

Allen et al (1966)

Ha and Allen(1967)

lA

1 \

VB

SCF

Extend. GTF lobe

GTF lobe AO

** Repulsive curve

v Repulsive curve

Reference State Description of Method Basis Set E(R) R

Schwartz (1967) h*. SCF GTF y

R =R

out in

1.6 -1.7443

Schwartz (1967)

Stevens (1967b)

Peyerimhoff et al (1966)

Joshi (1967)

lZ£ SCF

°2g

^2g

SCF

OC-SCF

GTF

DZ (s)

Extend. GTF

Extend. STF

\S R =R. out in

L.6 -2.1669

*S 2.437 -2.0785

•" 2.34 -2.0683

2.54 -16.2540 •" 2.500 -16.1440

41
Reference Description of Method Basis Set E(R)

BHKaufman and Burnelle(1966)

Peyerimhoff et al (1966)

Palke and Llpscomb(1966)

Palke and Lipscomb(1966)

Joshi (1967)

1 SCF

SCF

SCF

SCF

OC-SCF

Extend. GTF 2.243 -26.3734

Extend. GTF lobe 2.31 -26.3652

Min. STF 2.25 -26.3377

Optimized Min. STF 2.25 -26.3517

Extend. STF v^ 2.191 -26.2358

ciT Herman et al (1966)

Peyerimhoff et al (1966)

Joshi (1967)

Kari and Csizmadia(1967)

Bunau et al (1967)

X A OC-SCF

SCF

OC-SCF

SCF

SCF

Extend. STF

Extend. GTF lobe

Extend. STF

Extend. GTF

Extend. GTF

2.013 -39.0189

2.10 -39.2346

2.032 -39.1178

1.95 -39.2173

2.05 -39.1440

Reference State Description of Method Basis Set E(R) R

Morokuma and Pedersen (1967) 2^"

1 Hackmeyer and Whitten (1967) 2,"

CH

3

SCF

SCF Hartree-Fock

GTF

Extend. GTF lobe

2.041

2.00

-39.1933

-39.5394

Rutledge and Satumo (1965) L A

Fink et al (1967)

Ritter (1967)

Kari and Csizmadia (1967b)

Ritchie and King (1967b)

1.

1a'

OC-SCF Extend. STF

SCF GTF lobe AO

OC-SCF Extend. STF

SCF Hartree--Fock Extend. GTF

SCF Extend. GTF

1.935 -39.2361

H-.T

2.0

111° -39.3801

2.013 -39.2734

1.95, -39.4799

115

212 4 109 23

K -39.4633

Morokuma and Pedersen (1967) ^A SCR

CF

2.513, -332.5690

15°

42
Reference State Description of Method Basis Set E(R)

Kaldor and Shavitt (1966) SCF Bond orbitals 120° 1.967 -55.7641

Bishop et al (1963)

Reeves and Harrison (1963)

Moccia (1964b)

Joshi (1965)

Rajagopal (1965)

Bishop (1966)

Kaldor and Shavitt (1966a)

Rutledge and Saturno(1966)

Fink et al (1967)

Ritchie and King (1967b)

Snyder (1967)

OC-SCF

SCF

OC-SCF

SCF - Hartree Fock

OC-SOC

SCF

OC-SOC

Min. STF i. 1.9161 -55.6052

GIF M 106 °48' 1.9162 -54.1144

Extend. STF U 108°54' 1.928 -55.97482

E-xtend. STF V- 109*34'

1.867 -56.08419

Extend. STF -.Q 109°30' 1.9053 -56.2268

Extend. STF <y 104°10' 1.8592 -55.8698

DZ STF ^,T v^ 106°48' 1.910 -56.0992

Extend. STF s 120° 1.823 -56.0222

GTF lobe A0 M 115° 1.91 -56.1464

Extend. GTF 105° 1.903 -56.2015

Extend. GTF M 106°44' 1.91638 -56.183

Ueference Description of : fe t oc Bas 's Set E(R)

Grahn (1962)

Bishop (1965)

Moskowitz and Harrison (1965)

Fink et al (1967)

SCF

SCF

Extend. STF

Extend. GTF

GTF lobe AO

V

12) -76 • 174 1.80

U5°5' -76 .0184 1.30

120° -76 .3203

1.3

12J" -76 .2669 1.33

Moccia (1964b)

Boyd and Lipscomb (1967)

OC-SCF

SCF

Extend. STF

Ilin. STF+3d

89°48' 2.672

93° 22' 2.633

-341.3960

-341.3094

McLean (1960)

Moskowj.tz (1?65)

Min. STF

Extend. GTF

2.002, -76.5433

2.281

2.002, -76.760

2.281

43
State Description of Method Basis Set E(R) R

Buenkev et al (1967a)

McLean and Yoshi.mi::e (1967)

V

HCCH

SCF Hartree-Fock

Extend. GTFlobe

B/W-P Q.q

2.002, -76.7916

2.272

2.002, -76.3540

2.281

Newton and Palke(l966)

Buenker and Whittan(1967)

SCF

SCF

Hin. STF \i

Extend. GTF lobe M

-113.4496

-113.8094

Reference State Description of Method Basis Set E(R) E B79

Kaldor and Shavitt (1966b) l A]_ Davidson and Allen (1967) L A,

1 Pedersen and Morokuma(1967) k\

Veillard (1967) 1Z

+

McLean and Yoshimine(1967) 1I+

H2°2

SCF Scaled Min. STF U •

dihedral ar 120°igle -150.1565

SCF Extend. GTF lobe v^ 180° -150.7004

SCF LiCCHGTF V^ 150° -149.28845

SCF BA + P |J 3.55, 2.2696, 2.0088

-83.7305

FCCH

^,Q,q 2.417,

2.264, 1.990

-175.7236

McLean and Yoshimine(1967) l£t- SCF

C1CCH

u.Q.q 3.084, 2.288, 1.988

-535.7673

44
Reference State Description of Method Basis Set

Csizmadia et al (1966) \

McLean and Yoshimine (1967) £T SCF

HCOF

(CN)

Extend. GTF

BA+P

P E(R) R

vM,0,q 2.186, 2.o08

-212.1139

Burnelle and Kaufman(1967) l k

± SCF GIF 2.591,

102° 9' -348.8037

State Description of Method Basis Set E(R) R

Krauss (1964)

Hegstrom et al (1967)

Fink et al (1967)

SCF

SCF

SCF

Extend. GTF

Optimized Min. STF

GTF lobe AO

•* 2.35 -26.946

2.372 -26.9232

2.35 -26.9490

CH,

Nesbet(1960)

Saturno and Parr (1960)

Albasiny and Cooper (1961)

Krauss (1963)

Woznick (1964)

Sinai (1964)

Rutledge and Saturno(1965)

Klessinger and McWeeny

(1965)

Fink et al (1967)

Ritchie and King (1967a)

Snyder (1967)

1,A SOC-MO GTF

S0C-0C STF

SCF-OC Numerical

SCF Extend. GTF

SCF Extend. STF

SCF Min. STF

SOC-OC Extend. STF

Group c rbital Min. STF

SCF GTF lobe AO

SCF Hartree-Fock Extend. GTF

SCF Extend. GTF

2.0665 -39.1742

i.i -39.804

2.00 -39.90

2.0665 -40.1668

2.0665 -40.1810

2.0 -39.863

-39.859

2.067 -40.092

2.04 -40.1711

2.12 -40.1S83

2.0665 -40. 18 -J

45
Reference State Description of Method Basle Set E(R)

Grein (1962)

Krauss (1963)

Moccia (1964b)

Rajagopal(1965)

Fink et al (1967)

lA OC-SCF

SCF

OC-SCF

SCF

SCF

Min. STF

Extend. GTF

Extend. STF

Extend. STF

GTF lobe AO

IU.P S 1.835 -55.684

1.94 -56.504

1.990 -56.2177

1.905 -56.5216

1.98 -56.4996

Moccia (1964o)

PH+

4

L A OC-SCF Extend. STF 2.750 -341.5493

Moccia (1964a) \

SiH+

4 Extend. STF -290.1024

a. R is the inverse square root of the expectation value of i/R . Comparison can be made to the experimental r rotational constant B for t^ie zeroth vibrational level.

o

b. Upper bound result. Extrapolated results are significantly lower. This calculation

cannot be summarized simply and reference must be made to the original article for even a minimal description of the method.

46
(1958)

Sutton, L. E. (1958), Tables of Interatomic Distances, London, The Chemical Society

(1959)

Boys, S. F. and Shavitt, I. (1959), U. of Wisconsin NRL Technical Report WIS-AF-13

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Padgett, A. A- and Griffing, V. (1959), J. Chem. Phys. _30 2

_ 1286

Platas, 0., Hurst, R. P., and Matsen, F. A. (1959), J. Chem. Phys. 31 501

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Foster, J. M. and Boys, S. F. (1960), Revs. Modern Phys. 32, 305

Kolos, W. and Roothaan, C. C. J. (1960), Revs. Modern Phys. 32± 23°

Krauss, M. and Ransil, B. J. (1960), J. Chem. Phys. _33_j_ 840

Lefebvre-Brion, H., Moser, C. M., and Nesbet, R. K. (1960), J. Chem. Phys. _33j_ 931

McLean, A. D., (1960), J. Chem. Phys. ,32^ 1595

McWeeny, R. and Ohno, K. A. (1960), Proc. Roy. Soc. (London) A255, 367

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Albasiny, E. L. and Cooper, I. R. A. (1961), Mol. Phys. 4, 353

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Grahn, R. (1961), Arkiv Fysik 19, 147 47
Hijikata, K. (1961), J. Chem. Phys . 34, 221 Lefebvre-Brion, H., Moser, C, and Nesbet, R. K. (1961a), J. Chem. Phys. 34, 1950

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Browne, J. C. and Matsen, F. A. (1962), J. Phys. Chem. _66, 2332

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Clementi, E. (1962b), J. Chem. Phys. _36_l 750

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Clementi, E. and McLean, A. D. (1962a), J. Chem. Phys. _36, 45

Clementi, E. and McLean, A. D. (1962b), J. Chem. Phys. _36, 563

Clementi, E. and McLean, A. D. (1962c), J. Chem. Phys. J36j_ 745

Davidson, E. R. and Jones, L. L. (1962a), J. Chem. Phys. _37, 1918

Davidson, E. R. and Jones, L. L. (1962b), J. Chem. Phys. _37, 2966

Ebbing, D. D. (1962), J. Chem. Phys. 3bj_ 1361

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Moccia, R. (1962), J. Chem. Phys. 37, 910

48
Nesbet, R. K. (1962), J. Chem. Phys. J36, 1518

Phillipson, P. (1962), Phys. Rev. 125, 1981

Scheel, N. and Griffing, V. (1962), J. Chem. Phys. 36, 1453

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Anex, B. G. (1963), J. Chem. Phys. _38, 1651 Bishop, D. M. (1963), Mol. Phys. 6, 305 Bishop, D. M., Hoyland, J. R., and Parr, R. G. (1963), Mol. Phys. 6± 467

Carlson, K. D. and Moser, C. M. (1963), J. Phys. Chem. _67, 2644

Clementi, E. and McLean, A. D. (1963), J. Chem. Phys. _39, 323 Hagstrum, S. and Shull, H. (1963), Revs. Modern Phys. 3_5_, 624

Harris, E. G. and Taylor, H. (1963), J. Chem. Phys. .38, 2591

Kahalas, S. L. and Nesbet, R. K. (1963), J. Chem. Phys. _39, 529

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Krauss, M. (1963), J. Chem. Phys. JBJ^ 564

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McLean, A. D. (1963a), J. Chem. Phys. 38, 1347

McLean, A. D. (1963b), J. Chem. Phys. _39, 2653

Michels, H. H. and Harris, F. E. (1963), J. Chem. Phys. _39, 1464

Miller, R. V. and Present, R. D. (1963), J. Chem. Phys. 38, 1179

Moskowitz, J. W. (1963a), J. Chem. Phys. J38, 677

Moskowitz, J. W. (1963b), J. Chem. Phys. 39, 1557

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Poshusta, R. D. and Matsen, F. A. (1963), Phys. Rev. 132, 307

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Reeves, C. M. and Harrison, M. C. (1963), J. Chem. Phys. 39, 11

49
Roberts, C. S. (1963), Phys. Rev. 131, 203

Taylor, H. S. (1963a), J. Chera. Phys. 39, 3375

Taylor, H. S. (1963b), J. Chem. Phys. _39, 3382

(1964)

Browne, J. C. (1964a), J. Chem. Phys. 40, 43

Browne, J. C. (1964b), J. Chem. Phys. 41, 1583

Browne, J. C. (1964c), J. Chem. Phys. 41, 3495

Browne, J. C. and Matsen, F. A. (1964), Phys. Rev. 135, A1227

Carlson, K. D. and Nesbet, R= K. (1964), J. Chem. Phys. 41, 1051

Christoffersen, R. E. (1964), J. Chem. Phys. 41, 960

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Conroy, H. (1964b), J„ Chem. Phys. 41, 1341

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Goodisman, J. (1964), J. Chem. Phys. 41, 3889

Grahn, R. (1964), Arkiv Fysik 28, 85

Harris, F. E. and Taylor, H. S. (1964), Physlca _30, 105

Harrison, M. C. (1964), J. Chem. Phys. 41, 499

Hoyland, J. R. (1964), J. Chem. Phys. 41, 1370

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Kolos, W. and Wolniewicz, L. (1964b), J. Chem. Phys. 41, 3674

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Lefebvre-Brion, H, Moser, C. M., and Nesbet, R. K. (1964), J. Mol. Spectry. 13, 418

McLean, A. D. (1964), J. Chem. Phys. 40^ 2774

50
Moccia, R. (1964a), J. Chem. Phys. 40, 2164

Moccia, R. (1964b), J. Chem. Phys. 40^ 2176

Moccia, R. (1964c), J. Chem. Phys. 40^ 2186

Nesbet, R. K. (1964a), J. Chem. Phys. 40, 3619

Nesbet, R. K. (1964b), J. Chem. Phys. 41, 100

Preuss, H. (1964), Mol. Phys. 8^ 233

Ransil, B. J. (1964), unpublished work University of Chicago

Rosenfeld, J. L. J. (1964), J. Chem. Phys. 40, 384

Sinai, J. J. (1964), J. Chem. Phys. 40, 3596

Stevens, R. M. and Lipscomb, W. N. (1964a), J. Chem. Phys. 40, 2238

Stevens, R. M. and Lipscomb, W. N. (1964b), J, Chem. Phys. 41, 184

Stevens, R. M. and Lipscomb, W. N. (1964c), J. Chem. Phys. 41, 3710

Stuart, J. D. and Matsen, F. A. (1964), J. Chem. Phys. 41, 1646

Taylor, H. S. and Harris, F. E. (1964), Mol. Phys. ]_, 287

Wahl, A. C. (1964), J. Chem. Phys. 41, 2600

Woznick, B. J. (1964), J. Chem. Phys. 40, 2860

Yoshimine, M. (1964), J. Chem. Phys. 40, 2970

(1965)

Allen, L. C, Erdahl, R. M., and Whitten, J. L. (1965), J. Am. Chem. Soc. _87, 3769

Bishop, D. M. (1965), J. Chem. Phys. 43, 4453

Browne, J. C. (1965), J. Chem. Phys. 42, 1428

Burnelle, L. and Kaufman, J. J. (1965), J. Chem. Phys. 43, 354

Carlson, K. D. Ludena, E., and Moser, C. (1965), J. Chem. Phys. 43, 2408

51
Conroy, H. and Bruner, B. L. (1965), J. Chem. Phys. 42_, 4047

Edmiston, C. and Krauss, M. (1965), J. Chem. Phys. 42, 1119

Ebbing, D. D. and Henderson, R. C. (1965), J. Chem. Phys. 42, 2225

Gerhauser, J. and Taylor, H. S. (1965), J. Chem. Phys. 42, 3621

Goodisman, J. (1965), J. Chem. Phys. 43, 3037

Huo, W. M. (1965), J. Chem. Phys. 43, 624

Huzinaga, S. (1965), J. Chem. Phys. 42, 1293

Joshi, B. D. (1965), J. Chem. Phys. 43, S40

Kern, C. W. and Karplus, M. (1965), J. Chem. Phys. 42, 1062

Klessinger, M. and McWeeny, R. (1965), J. Chem. Phys. 42, 3343

Kolos, W. and Wolniewicz, L. (1965), J. Chem. Phys. 43_, 2429

Krauss, M. and Mies, F. H. (1965), J. Chem. Phys. 42, 2703

Larson, E.G. and Thorson, W. R. (1965), J. Chem. Phys. 43, 3832

Lefebvre-Brion, H. and Moser, C. M. (1965), J. Mol. Spectry. 15, 211

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Moskowitz, J. W. (1965), J. Chem. Phys. 43, 60; (See errata J. Chem. Phys. 45,2338 (1966))

Nesbet, R. K. (1965), J. Chem. Phys. 43, 4403

Peyerimhoff, S. (1965), J. Chem. Phys. 43, 998

Rajagopal, P. (1965), Z. Naturforsch. 20a, 1557

Rutledge, M. and Saturno, F. (1965), J. Chem. Phys. 43, 597

Sahni, R. C. and DeLorenzo, E. J. (1965), J. Chem. Phys. 42, 3612

Schneiderman, S. B., and Michels, H. H. (1965), J. Chem. Phys. 42, 3706

Schulman, J. M., and Moskowitz, J. W. (1965), J. Chem. Phys. 43, 3287

Stevens, R„ M. and Lipscomb, W. N. (1965a), J. Chem. Phys. 42, 3666

Stevens, R. M. and Lipscomb, W. N. (1965b), J. Chem. Phys. 42, 4302

Wakefield, C. and Davidson, E. R. (1965), J. Chem. Phys. 43_j_ 834

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52
(1966)

Allen, L. C. (1966), "Quantum Theory ofAtoms, Molecules, and the Solid State," edited

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Bishop, D. M. (1966), J. Chem. Phys. 45, 1787

Bishop, D. M. and Randic, M. (1966), J. Chem. Phys. 44, 2480

Browne, J. C. (1966a), J. Chem. Phys. 44, 835

Browne, J. C. (1966b), J. Chem. Phys. 45, 2707

Buenker, R. J. and Peyerimhoff (1966), J. Chem. Phys. 45, 3682

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Institute

Csizmadia, I. G. (1966), J. Chem. Phys. 44, 1849

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6^ 217

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Fougere, P. F. and Nesbet, R. K. (1966), J. Chem. Phys. 44, 285

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53
Herman, R. B., Lykos, P. G., Sharp-Ritter, J. D., and Moccia, R. (1966), "Quantum Theory

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Hoyland, J. R. (1966a), J. Chem. Phys. 45, 466

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Huo, W. M. (1966), J. Chem. Phys. 45, 1554

Joshi, B. D. (1966), J. Chem. Phys. 44, 3627

Kaldor, V. and Shavitt, I. (1966a), J. Chem. Phys. 45, 888

Kaldor, V. and Shavitt, I, (1966b), J. Chem. Phys. 44, 1823

Kaufman, J. J. and Burnelle, L. A. (1966), RIAS Tech. Rept. 65-11

Kestner, N. R. (1966), J. Chem. Phys. 45, 208

Kestner, N. A. and Sinanoglu, 0. (1966), J. Chem. Phys. 45, 194

Kolos, W. and Wolniewicz, L. (1966a), J. Chem. Phys. _45, 509

Kolos, W. and Wolniewicz, L. (1966b), J. Chem. Phys. 45, 944

LefebvrefBrion, H. and Moser, C. M. (1966), J. Chem. Phys. 44, 2951

Lester, W. A. and Krauss, M. (1966), J. Chem. Phys. 44, 207

Michels, H. H. (1966), J. Chem. Phys. 44, 3834

McLean, A. D. and Yoshimine, M. (1966), J. Chem. Phys. 45, 3676

Menna, E., Moccia, R., and Randaccio, L. (1966), Theoret . Chim. Acta 4, 408

Michels, H. H. (1966), J. Chem. Phys. 44, 3834

Moskawitz, J. W., Newmann, and Harrison, M. C. (1966) "Quantum Theory of Atoms, Molecules,

and the Solid State," edited by P. o. Lowdin (Academic Press Inc., H*w York) p. 227

54
Newton, M. D. and Palke, W. E. (1966), J. Chem. Phys. _45, 2329

Palke, W. E. and Lipscomb, W. N. (1966a), J. Am. Chen. Soc. _88, 2384

Palke, W. E. and Lipscomb, W. N. (1966b), J. Chem. Phys. 45, 3948

Pearson, A. G., Poshusta, R. D., and Browne, J. C. (1966), J. Chem. Phys. 44, 1815

Peyerimhoff, S. D. Buenker, R. J., and Allen, L. C. (1966), J. Chem. Phys. 45, 734

Richards, W. G., Verhaegen, G., and Moser, C. M. (1966), J. Chem. Phys. _45, 3226

Ritchie, C. D. and King, H. F. (1966), J. Am. Chem. Soc. _88, 1069

Rothenberg, S. and Davidson, E. R. (1966a), J. Chem. Phys. _44, 730

Rothenberg, S. and Davidson, E. R. (1966b), J. Chem. Phys. 45, 2560

Rutledge, R. M. and Saturno, A. F. (1966), J. Chem. Phys. 44, 977

Scott, D. R., Greenwalt, E. M., Browne, J. C, and Matsen, F. A. (1966), J. Chem. Phys.

44, 2981

Veillard, A. (1966), Theoret. Chim. Acta 5, 413

Verhaegen, G., and Richards, W. G. (1966), J. Chem. Phys. 45, 1828

Wahl, A. C. (1966), Science 151 , 961 Whitten, J. L. (1966), J. Chem. Phys. 44, 35

J

Wolniewicz, L. (1966), J. Chem. Phys. 45, 515

(1967)

Barnett, G. P. (1967), Can. J. Phys. 45, 137

Basch, H. (1967), unpublished results Bell Telephone Laboratories

Bender, C. F. and Davidson, E. R. (1967a), J. Chem. Phys. 47, 360

Bender, C. F. and Davidson, E. R. (1967b), J. Chem. Phys. 46, 3313

Bender, C. F. and Davidson, E. R. (1967c), to be published

Bertoncini, P. and Wahl, A. C. (1967), unpublished work PhD thesis Bertoncini,

University of Wisconsin)

Boyd, D. B. and Lipscomb, W. N. (1967), J. Chem. Phys. 46, 910

Buenker, R. J., Whitten, J. L., and Allen, L. C. (1967), to be published J. Chem. Phys.

Buenker, R. J., and Whitten, J. L. (1967), unpublished results

Buenker, R. J., Peyerimhoff, S. D„, and Whitten, J. L. (1967a), J. Chem. Phys. 46, 2029

Buenker, R. J., Peyerimhoff, S. D., and Whitten, J. L. (1967b), unpublished results

55
Bunau, G., Dlercksen, G., and Preuss, H. (1967), to be published

Burnelle, L. and Kaufman, J. J. (1967), unpublished results RIAS

Cade, P. E. and Wahl, A. C. (1967), to be published

Cade, P. E. and Huo, W. M. (1967a), J. Chem. Phys. 47, 614

Cade, P. E. and Huo, W. M. (1967b), J. Chem. Phys. 47, 649

Cade, P. E. (1967a), to be published

Cade, P. E. (1967b), Proc. Phys. Soc. (London) 91, 842

Carlson, K. D. and Moser, C. (1967), J. Chem. Phys. 46, 35

Cheetham, C. J. and Richards, W. G. (1967), unpublished results Physical Chemistry

Laboratory, Oxford

Clementi, E. (1967a), IBM Research Paper RJ-411 2/6/67

Clementi, E. (1967b), IBM Research Paper RJ-416 2/8/67

Clementi, E. (1967c), IBM Research Paper RJ-418 2/8/67

Clementi, E. (1967d), IBM Research Paper RJ-415 2/8/67

Considine, J. P. and Hayes, E. F. (1967), to be published

Das, G. (1967), J. Chem. Phys. 46, 1568

Das, G. and Wahl, A. C. (1967), to be published J. Chem. Phys.

Davidson, R. and Allen, L. C. (1967), unpublished results Princeton University

Edndston, C. and Krauss, M. (1967), unpublished results

Erdahl, R. M. (1967), PhD. thesis Princeton University

Erdahl, R. M., Harrison, J. F., and Allen, L. C. (1967), to be published

Fink, W. H. and Allen, L. C. (1967), J. Chem. Phys. to be published

Fink, W. H. and Allen, L. C. (1967a), J. Chem. Phys. 46, 2261

Fink, W. H. and Allen, L. C. (1967b), J. Chem. Phys. 46, 2276

Fink, W. H., Whitten, J. L., and Allen, L. C. (1967), J. Chem. Phys. to be published

Fink, W. H., Pan, D. D., and Allen, L. C. (1967), J. Chem. Phys. to be published

Geller, M., Sachs, L., and Kaufman, J. J. (1967), unpublished results

RIAS and Jet Propulsion Laboratory

Gilbert, T. L. and Wahl, A. C. (1967a), to be published (Bull. Am. Phys. Soc. 10, 1097 (1965)

Gilbert, T. L. and Wahl, A. C. (1967b), to be published

Gilbert, T. L. and Wahl, A. C. (1967c), to be published

Ha, T. K. and Allen, L. C. (1967), unpublished results Princeton University

Hackmeyer, M. and Whitten, J. L. (1967), unpublished results

Harris, F. E. and Michels, H. H. (1967), to be published Int. J. Quantum Chemistry

Slater Symposium Issue

Harrison, J. F. (1967), PhD. Thesis Princeton University

Harrison, J. F. and Allen, L. C. (1967), to be published

56
Hayes, E. F. (1967), to be published

Hegstrom, R. A., Palke, W. E., and Lipscomb, W. N. (1967), J. Chem. Phys. 46, 920

Horsley, J. A. and Richards, W. G. (1967), unpublished results Physical Chemistry

Laboratory, Oxford

OQO

Huo, W. M., Freed, K. F., and Klemperer, W. (1967), J. Chem. Phys „ 46, 3556

Janoschek, R., Preuss, H., and Diercksen, G. (1967a), to be published

Janoschek, R., Preuss, H., and Diercksen, G. (1967b), to be published

Joshi, B. D. (1967), J. Chem. Phys. 46, 875

Kapral, R. (1967), J. Chem. Phys. 46, 2317

Kari, R. E. and Csizmadia, I. G, (1967), J. Chem. Phys. 46, 1817

Kaufman, J. J. and Burnelle, L. A. (1967), RIAS Technical Report 65-11

Kolos, W. and Wolniewicz, L. (1967), J. Chem. Phys. 46, 1426

LMSS (1967), out put of Laboratory of Molecular Structure and Spectra, University of Chicago under the direction C.C.J. Roothaan. Attribution to each calculation was

not given but the following individuals have contributed: P. E. Cade, J. Greenshields,

W. M. Huo, G. L. Malli, K. D. Sales, and A. C. Wahl

McLean, A. D. and Yoshimine, M. (1967), to be published, see J. Chem. Phys. 46, 3682

and Supplement to IBM Journal Res. and Dev. 11/67

Matcha, R. L. and Nesbet, R. K. (1967), to be published

Matsumoto, G. H., Bender, C. F., and Davidson, E. R. (1967), J. Chem. Phys. 46, 402

Mate-he, R. L. (1967), to be published

Michels, H. H. (1967), unpublished results United Aircraft Research Laboratories

Miller, K. and Krauss, M. (1967), unpublished results

Morokuma, K. and Pedersen, L. (1967a), unpublished results

Morokuma, K. and Pedersen, L. (1967b), unpublished results

Morris, B. M. and Present, R. D. (1967), J. Chem. Phys. 46^ 653

O'Hare and Hurst (1967), J. Chem. Phys. 46, 2356

Pan, D. C. and Allen, L. C. (1967), J. Chem. Phys. 46, 1797

Pedersen, L. and Morokuma, K. (1967), to be published J. Chem. Phys.

Peyerimhoff, S. (1967), unpublished results (Princeton University)

Peyerimhoff, S. D. and Buenker, R. J. (1967), J. Chem. Phys. to be published

Peyerimhoff, S. D., Buenker, R. J., and Whitten, J. L. (1967), J. Chem. Phys. 46, 1707

Pfeiffer, G. V. (196 7), unpublished results Princeton University

Preuss, H. and Diercksen, G. (1967), unpublished results

Richards, W. G. (1967), Trans. Faraday Soc. 63, 530

57
Richards, W. G., Verhaegen, G., and Moser, C. M. (1967), unpublished results

Physical Chemistry Laboratory, Oxford and Centre de Mecanique Ondulatoire Appliguee, Paris

Ritchie, CD. and King, H. F. (1967a), to be published J. Chem. Phys.

Ritchie, C. D. and King, H.F. (1967b), unpublished results State University New York at Buffalo

Ritter, J. D. (1967), private communication to Kari and Csizmadia

Rothenberg, S. and Davidson, E. R. (1967), J. Mol. Spectroscopy 22, 1

Sales, K. D., Cade, P. E., and Wahl, A. C. (1967), to be published

Sanders, W. and Krauss, M. (1967), unpublished results

Schwartz, M. E. (1967), thesis Vanderbilt University

Shavitt, I., Stevens, R. M., Minn, F. L., and Karplus, M. (1967), to be published

Snyder, L. C. (1967), J. Chem. Phys. 46, 3602

Stevens, R. M. (1967a), unpublished result Harvard University

Stevens, R. M. (1967b), unpublished result Harvard University

Veillard, A. (1967), unpublished work

Verhaegen, G. and Richards, W. G. (1967), Proc . Phys. Soc. 90, 579

Verhaegen, G., Richards, W. G., and Moser, C. M. (1967a), J. Chem. Phys. 4£, 160

Verhaegen, G., Richards, W. G., and Moser, C. M. (1967b), to be published J. Chem. Phys.

Wahl, A. C, Bertoncini, P. J., and Gilbert, T. L. (1967), unpublished results

Walker, T.E.H. and Richards, W. G. (1967), unpublished results Physical Chemistry

Laboratory, Oxford

Whitten, J. L. and Allen, L. C. (1967), to be published

Whitten, J. L., Petke, J. D., and Bueriker, R. J. (1967), unpublished results

Whitten, J. L. and Buenker, R. J. (1967), unpublished results

Experimental and Hartree-Fock Atomic Energies

Atom

He

Li

Be

B

C

N

State

'1/2

Pl/2

Po

S3/2

a Hartree-Fock

2.86168

7.43272

14.57302

24.52905

37.68861

54.40091

74.80936

-E

Experimental

2.90372°

7.4780

14.6685

24.6579

37.8558

54.6122

75.1101

"P3/2 99.40928

58

99.8053
Experimental and Hartree-Fock Atomic Energies

Atom State Hartree-Fock a Experimental13

Ne

1

S 128.54701 129.056

2 Na Si/2 161.85889 162.441

Mg

1

S 199.61458 200.333

Al 2Pi/2 241.87665 242.752

Si

3 Po 288.85426 289.927

P 4

S3/2 340.71866 342.025

S

3 P

2 397.5C475 399.144

2 CI P3/2 459.48201 461.514

Ar 1 S 526.8175 529.303

a. Clementi, E. (1965). Tables of Atomic Functions,

Supplement to IBM J. Res. Develop. 9, 2.

b. Cade and Huo (1967a, b). The analysis of the recommended "experimental"

values is given in detail. For the rough comparison with molecular energies

for which this table is included these values are mors than adequate.

c. Peke^is, E. (1958), Phys. Rev. 112 , 1649.

Atomic Unit Conversions

E la.u. (Hartree) = 27.20976 eV

O R la.u. (Bohr) = 0.529172 A

I Q

|i la.u. = 2.54158 10 esu cm (Debye)

6 la.u. = 1.34492 10

-2 esu cm

2

q la.u. = 3.24140 10 esu/ cm 3

59
C. One electron properties : Introduction

The results of a selected set of diatomic calculations are given for the dipole moment and derivative, the quadrupole moment, and the field gradients. The results are in cgs units: |i in Debyes, 10" esu cm, |_i' in 10 esu,

9 in 10 esu cm , and q in 10 esu/cm . When available experimental values

are included. These are not referenced and were obtained for the most part from the theoretical paper that is referenced.

The polyatomic tables do not include the derivative of the dipole moment

-5 2 but the Larmor susceptibility XL

in units of 10 erg/gauss mole is included. Note that such values are usually available in diatomic studies for which the quadrupole moment is given. The properties are defined as follows:

1. Dipole moment

M = £ ZA

d - e < z >

A

2. Quadrupole moment

9 = £ Z A d

2

- | e < 3z

2 -r2 >

A

A A 2

e

2 2

3 - \= -fr <r >

6mc

4. Field gradient

Only the q component of the field gradient is tabulated here. a

3cos29

A13 - 1 3cos

2

6. - 1

„ _ v 7 AB A

q, = i \ 7. - e < ~ >

A b B ,3 3 <L r.

For the first three properties all distances are measured from a common origin which is commonly chosen to be the center of mass or the centroid of charge. Consideration of the gauge is discussed by McLean and Yoshimine (1966) who also illustrate the interrelations which exist between properties which

depend on the square of the electronic coordinates. Note that some authors have not selected the center of mass as origin in determining the quadrupole

moment and those cases are noted. Polarity of (J. is defined positive for A B and H A . The field gradient is determined in a coordinate system relative to the atom in question.

a. The field gradient tensor has been calculated ab initio only for formaldehyde. See Lowe and Flygare (1964), J. Chem. Phys. 41, 2153; Flygare et al (1966), J. Chem. Phys. 45j 2793.

60
Molecule

and State

c

xn cowne (196 la)

Browne (1964b)

McLean and Yoshiinine (1966)

Exp

Kolos and Wolniewicz (1966b) 1.54 10

-6.697 0.209

-3.102 0.223

-46.32 0.259

-47.13 0.259

0.477

0.460

xV" Ebblng (1962) -5.96

Kahalas and Nesbet (1963) -5.388

Browne and Matsen (1964) -5.93

Bender and Davidson (1966) -5.965

Csizinadia (1966) -6.008

Cade and Huo (1966) -6.002

Exp. -5.38

-0.108

-0.112

-0.113 0.149

-2.0

Molecule

and Reference

kV" Cade and Huo(1966)

X

1^

X

1^

h

V

i«

Cade and Huo (1966)

Harrison (1967)

1.733

1.584

0.295

1.196

-0.338

-0.864

-3.366 -1.823 0.549

0.06l

a -0.332 0.927

1.289

3 0.067 0.566

5.075

3 1.853 0.989

4.768

3 1.866 0.967

x

2nr Cade and Huo(1966)

Exp

1.570

1.46

61
Molecule

and State

X

3IT

X

3!"

X

3!"

lA

1 +

z

3n

in

Joshl (1965)

Cade and Huo(1966)

Harrison (1967)

Huo(1966)

1.931

1.627

1.016

0.989

0.869

1.294

1.65

1.38

1.85 A Cade and Huo(1966)

Exp

OH

1.780

1.66

Molecule

and State Reference <U

X

1^

FH

Nesbet(1962) 1.827

Clementl(1962) 1.984

Moccia (1964) 2.014

Cade and Huo(1966) 1.942

Moskowitz et al(1966) 1.921

Erdahl et al(1967) 2.008

Whltten and Allen(1967) 1.98

Bender and Davidson (1967) 1.649

McLean and Yoshimine (1967) 1.934

Exp 1-82

2.539 9.299

2.390

3 10.48

2.325

8.720

9.313

1.771

1.769

1.694

Cade and Huo(1966) -6.962

xV Cade and Huo(1966)

MgH

-1.516

62
Molecule

and State

<ll <5z

Cade and Huo(1966)

« 2n Cade and Huo(1966) 0.302

x\:~ Cade and Huo(1966)

HI

0.538

x

2n. Cade and Huo(1966) 0.861

X

1^

C1H

Moccia(1962) 2.166

Nesbet(1964b) 1.488

Cade and Huo(1966) 1.197

Menna et al (1966)

McLean and Yoshimlne (1967) 1.215

Exp 1.08

1.788 3.957

3.61

3.744 11.55 0.908

Molecule

and

State n

1 e

Hi

tt Poshusta and Matsen(1963) 7.625

Li. X^ LMSS(1967) 13.886 -0.0162

LMSS(1967) 1.582 0.365

*S

LMSS(1967)

LMSS(1967)

3.733 2.706

-4.960 -4.156

Nesbet (1964a)

LMSS(1967)

-1.221

-1.264 -4.411

63
Molecule

and

State Reference H n' 6

N

2+

X

2

Z*~ LMSS(1967) 4.246 2.256

2 A Ily LMSS0967) 1.845 -5.755

xV8 LMSS(1967) -0.376 4.483

X

1^

Wahl(1964) 0.886 22.262

X L„ LMSS(1967) 13.984

Molecule

and State Reference

LiF

X

lL+ McLean(1964) 6.30 4.08

8 Pfeiffer(1967) 6.23 3.95 -0.089

McLean and Yoshimine (1967) 6.295 5.769 -0.118 -0.896

Exp 6.28 4.35 -0.128

LiCl

x

l£+ Matcha (1967) 7.256 2.30 -0.063 -0.399

Exp 7.13 2.3

LiBr

x

l£+ Matcha (1967) 6.98 -0.069 -1.433

Exp 7.27

BeO

X

l£* Yoshimine (1964) 7.290

McLean and Yoshimine (1967) 7.353 6.354 -2.824 -0.161

64
Molecule

and

State Reference

x

1^

BF

Nesbet (1964a) -0.617

Huo (1965) -1-04

McLean and Yoshimine (1967) -0.883

5.56

4.382

4.53 b -1.753 1.702

4.18? -1.755 1.980

xir+

x

1^

Lefebvre-Brion et al (1963) 0.132

Nesbet (1964a) 0.361

Huo (1965) 0.274

McLean and Yoshimine (1966) C'0+

Huo (1966) 0.274

McLean and Yoshimine (1967) 0.280

Exp -0.112

Huo (1966) 2.46

K>:;. 1.38

-2.071

3.83 -1.306 -3.32 -2.201

4.39 -2.19

Analysis of sign of M

-2.14 -3.82 -2.201

-2. 20-4 -3.808 -2.348

2.97 ±1.63

1.07 0.016 3.153

Molecule

and

Richards (1967)

Exp

! ...

1.98

f!r+ Matcha (1967)

Exp

8.35

8.16

-1.224 -0.266

X

1^ Matcha (1967)

Exp

NaCl

9.10

9.00

-0.811 -0.648

X*E+

NaBr

Matcha (1967)

McLean and Yoshimine (1967)

-0.586 -0.162

17.5

65
Molecule

and State Reference ^' 6 q. *

^

MgO

McLean and Yoshimine (1967) 8.842 0.221 -0.517 6.321

V

A1F

McLean and Yoshimine (1967) 1.337 -6.713 -3.867 0.456

l& McLean and Yoshimine (1967) 3.397 -5.219 -7.952 -3.006

McLean and Yoshimine (1967) 3.241 -2.818 -7.828 -4.954

h

+

Stevens (1967)

Exp

C1F

1.099

0.88

Molecule

and Reference

Matcha (1967)

Exp

8.69

8.60

-1.962 -1.158

1D*- Matcha (1967)

Exp

KC1

10.46

10.27

-1.413 -0.326

V McLean and Yoshimine (1967) 10.946 -7.578 -0.846 -1.432

V

6r

Carlson et al (1965) 2.6

7.7

1.5

1.0

66
Molecule

and State M' 6 q q

1 2

*l+

ScF

Carlson and Moser(1967) 4.64

5.77

JA r

TiO

Carlson and Moser(1967) 5.93

4.25

X r+

RbF

Matcha (1967)

Exp

8.76

8.55

-2.813 -0.704

1 +

McLean and Yoshimine (1967) 10.207 -14.24 -0.805 -1.500

Molecule

and State Reference \

".."

Moccia (1964) 2.08

Moskowitz and Harrison (1965) 1.99

Fink et al (1967) 2.50

Exp 1.85 2.

Moccia (1964)

Exp

H S

2

1.72

0.97

*&

HCN

McLean and Yoshimine (1967) 3.292 2.710

Pan and Mien (1967) 3.37

Exp 2 . 98

1.027 -1.580 -3.903 -3.925

67
Molecule

and State Reference |J 8 q q q x

1 2 3 L

(FHF)" ^g McLean and Yoshimine (1967) -7.513 2.295 0.106 2.295 -8.S34

(0CN)~

1 +

McLean and Yoshimine (1967) 1.800 -10.87 3.078 -2.002 -0.770 -9.387

co

2

*£+ McLean and Yoshimine (1967) -5.281 2.446 -2.362 2.446 -9.021

Exp -3.

E+McLean and Yoshimine (1967) 0.638 -3.745 -1.284 -1.559 8.310 -8.604

Exp 0.167 -2.5

FCN ^ McLean and Yoshimine (1967) 2.279 -4.214 10.54 -0.476 -2.416 -9.567

Molecule

and

State Reference M 8 q q q 1 X

1 2 3 4 1

-16.83

(SCN)~

lE* McLean and Yoshimine (1967) 2.155 -11.47 5.500 -1.861 -1.424

SCO

1X+

McLean and Yoshimine (1967) 0.985 -1.479 6.417 -2.418 0.995 -16.02

C1CN y- McLean and Yoshimine (1967) 3.052 -3.828 15.27 -0.785 -3.145 -16.16

NH

3

*A X Moccia (1964b) 1.51

Joshi (1965) 1.52

Rajagopal (1965) 1.39 -0.270

a

Kaldor and Shavitt (1966a) 2.29

Fink et al (1967) 1.49

Exp 1.47

2 2

12+ McLean and Yoshimine (1967) 7.232 1.111 -1.236 -4.852

g

68
Molecule

and

State Reference U 9 q q q q y 21 2? _3 4 L

LiCCH

1E

f Veillard (1967) 6.166 21.08

HCCF

l£*~ McLean and Yoshimine (1967) 0.913 4.528 10.59 0.099 -0.621 1.173 -10.80

HCCC1

12Tf McLean and Yoshlmine (1967) 0.421 7.764 14.40 -0.329 -0.963 1.170 -17.64

!£+ McLean and Yoshimine (1967) -9.063 -4.049 -1.084 -19.48

Molecule

and State Reference M 6 q q q q q c

McLean and Yoshimine (1967) 4.126 4.480 -3.548 -1.196 -0.559 -1.335 1 . 105

a. Origin of coordinates at heavy mass.

b. Origin of coordinates at mid-point of molecule.

69
D. Static Polarizabilities : Introduction

Two different techniques have been used to obtain the polarizabilities.

A perturbation approach has been applied to a few molecules based on both zero-order H.F. and, in the case of H

2

, very accurate wave functions. These

are summarized in the table on Dl. The H work is very extensive and results

are reported for polarizabilities averaged over numerous vibration-rotation

levels.The second approach has been to solve the H.F. equations with the field

included in the Hamiltonian. Previous work in this direction has been reported

by Cohen and Roothaan ( J. Chem. Phys. 43, S34 (1965)) for atoms and a large

number of linear molecules has recently been treated by McLean and Yoshimine.

Their polarizability and hyperpolarizability tensor components are listed in the table on D2. Note the yand B columns are to be multiplied by the scale factor

at the top of the respective columns. Definitions and discussion of this procedure are referred to their publication and Buckingham (1959). Note

that, with the exception of HCN, all the values are reported for the molecular geometries listed in the References.

Reference Molecule O. a

XX zz

Kolos and Wolniewicz (1967) H 0.7022 1.0021

Stevens and Lipscomb (1964a) LiH O'Hare and Hurst (1967)

Stevens and Lipscomb (1964b) HF O'Hare and Hurst (1967)

Stevens and Lipscomb (1964c) F O'Hare and Hurst (1967)

O'Hare and Hurst (1967) N

Exp

McLean and Yoshimine (1967) CO O'Hare and Hurst (1967)

Exp

O'Hare and Hurst (1967) LiBF

-24 2 a. Units: 10 cm

4.063 3.35 5.080 3.35

0.623 0.859

0.791 1.002

0.77 2.15 0.949 2.248

1.954 4.046

1.45 2.38

2.11 2.088 3.222

1.625 2.60

40.649 59.848

3.738 2.716

70
Molecular Polarlzabilities

HF

HC1

LiF

BF

CO

NaBr

KC1

RbF

A IE

SiO

PN

SrO

HCNb

N2

(OCN)

FCN

SCO

a

zz

(3zzz

Yzzzz

IO 3

A

z zz

B zz zz

IO 2

3/2 C zz zz

8.07 -74. 31.6 -1.5 34.

23.4 -288. 1. 137. -5.7 i67.

8.40 27. •10 1 4. 38.5 -1.0 53.

23.6 57. 4. -33. -IO

1 -8. 513.

21.1 19. •io

1 1. -33. -6.1 203.5

45.4 6. •10 3 3. -IO 2 31. -8. -IO 1 39. -IO

1

39.7 31. •io 2 1. -io 2 44. -IO 1 1.-10 1 108. -IO 1

24.1 88

.

•io

1 16. -IO

1 57. -IO1

45. -8. •io

2 -6. -66. -101 -7. 106. -IO1

39.6 35. •IO 1 3. -49. -2. 58. -IO 1

49.7 15. •IO 1 215. -10.7 506.

62.3 1.-10 1 9.-10 2

33.2 2. •io 2 5. -94. -13. 36. -IO

1

40 .

6

3. •IO

2 8. -85. -4.6 38. -IO

1

41.1 -1. •io

2 17. -IO1 -3. 59. "IO

1

32.5 -1. •io

2 267. -2. 515.

G2.7 44. -6. 83.- IO

1

Molecular Polarlzabilities

Molecule a g v A B 3/2 C zz zzz zzzz z zz zz zz zz zz

10 J 10^

73.5

53.3 -14. •IO 1

46.4 -8. •io 2

76.1 -17. •io

2

95.

(SCN)

C1CN

FCCH

C1CCH

NCCCH

a. For notation see Buckingham, A.D. (1959), Quart. Rev. 13, 194

b. HCN R = 1.81287,

Entire table is due to McLean and Yoshlmine (1967) m-25 2 ,.-33 5, .,,,-40 7, 2 Units] a 10 cm , p 10 cm /esu, y 10 cm /esu

A 10"34cm

4

, B 10"41

cm

6 /esu, C 10~42

cm

5

28. •IO 1 -7. 114. •10*

378. -3.2 978.

6] . •io 1 -17. 107. •io 1

102. •io

1 -40. 207.

2.

•io

1

•io

3

71
E. Magnetic Constants : Introduction

This table slightly extends and updates a similar table in Nesbet's review

on H. F. calculations (Adv. Quant. Chem. , Vol. 3, 1967). It is provided as another test of the accuracy of one-electron properties of H. F. functions. All the calculations are based on perturbation of approximate H. F. functions.

Ground State Magnetic Constants of Diatomic Molecules

Molecule (AB) LiH Li

2 FH F

2

X(PPm> calc

obs

-7.630 -28.94 -10.27

-8.6

-10.617

a(ppm) calc

obs

90.15 98.58 404.65 -199.7

-210.1

a^ppm) calc

obs

26.45 28.11

27.9

C (kc/sec A:)calc 9.45 0.240 336.0 152.0

obs 9.92 + 305 157

C (kc/sec

B :)calc -9.15 -69.97

obs -10.1 + 71

|i /J(nm) calc -0.6677 0.1100 0.738 -0.101

obs -0.654 0.10797 0.7392 -0.121

18.75

-261.7

24.46

492.9

-14.92

-8.30

LiH- Stevens and Lipscomb (1964a)

Stevens and Lipscomb (1964b)

Hegstrom and Lipscomb (1966)

72
F. Spectroscopic Constants : Introduction

The results presented were obtained by a Dunham analysis of accurate

H. F. and, for the few electron diatomics, accurate beyond H. F. calculations:

Details of the fits will vary and in the case of H, extreme csre has gone into

the procedure. For the most accurate calculations the spectroscopic constants

are usually ignored and the vibration-rotation energy levels are calculated by numerical integration of the Schrodinger equation. Unfortunately, the accuracy of most calculations do not warrant an effort beyond the spectroscopic

constants. Nontheless, these results are considered the best obtainable for their type of calculation.

In order to facilitate comparison with experimental values, U) e

. lt) exe, B e

, ge are given In cm" and r in A. Experimental values are given when provided by the theoretical paper in question.

Molecule

and State Reference It ill X. e e e

2-152 41.91

2442.7 67.03

2429 36 . V0

2465.0 61.40

2351.0 58.56

2349.0 58.78

4398

4395.2

2354

2296

2502

2271

2734

2127

2230

2468

2389

2413

8 \

8

2s H+

8

3d

3s3d^

3s3p^

3pVu 2p\

3p

4f

Browne (1964a)

Sxp

Browne (1964a)

Exp

Browne (1964b)

Das and Wahl(1966)

Exp

Rothenberg and Davidson (1966b)

1.204

1.626

1.296

1.425

1.57

1.57

1.030

1.033

1.04

1.038

1.05

1.05

0.74

0.7416

1.009

1.073

1.042

1.064

1.060

1.0S5

1.096

1.031

1.048

1.058

73
Molecule

and State Reference

3d L n

s 3d 3no

3d

L A„

3 3d 48

X

1 ^ Baran and Kolos(1962)

McLean (1964)

Cashion (1966)

Exp

2286

2283

2354

2354

4401.4

4402.3

4402.744

4401.39

119.3 60.879

121.82 60.880

121.548 60.8550

120.82 60.864

1.063

1.063

1.053

1.053

0.7413

0.7412

0.741405

0.74116

C 1^

X

1 ^

b

l

x:+

a%+

Molecule

and State

Anex(1963)

Peyerimhof£(1965)

Wolniewicz (1965)

Michels(1966)

Reference

3286 0.765

3233 176 35.30 2.82 0.0770

0.774

3379 313.7 35.85 3.785 0.764

209.7 89.71 2.343 0.7977 2.990

381.8 6.535 1.038 0.01449 4.491

220.3 10.13 1.197 0.06081 4.183

373.0 99.62 3.739 0.8156 2.366

395.8 5.882 1.244 0.02724 4.103

225.5 6.595 1.255 0. 04136 4.085

uu x

e e

2v+

HeH

Michels and Harris (1963) 4065

4195

LiH

Browne and Matsen(1964) 1438

Cade and Huo(1967a) 1433

252

273

38.0

39.8

Exp. 1405.6

86

23.26 7.426

23.20 7.513

0.742

0.725

1.612

0.1945 1.605

0.213 1-595

BeH

Cade and Huo (1967a) 2147

Exp. 2058.6

34.60 10.392 0.2647 1-338

35.5 10.308 0.300 1.343

xV Cade and Huo (1967a)

Exp

BH

2499

2367.5

49.04 12.273 0.3726 1.797

49 12.016 0.408 1.611

CH

Cade and Huo(1967a) 3053

Exp 2868.5

74

55.50 14.882 0.4712 1.104

64.4 14.448 0.530 1.124
Molecule

and State

X

JE" Cade and Huo(1967a) 3556 66.78 17.319 0.575 1.017

16.668 0.646 1.033

X

3!:"

Cade and Huo (1967a) 3556

Exp 3125

Oil

Cade and Huo (1967a) 4062

Exp 3735.2

NaH

Cade and Huo (1967a) 1187

Exp 1172.2

X2 ^ Cade and Huo(1967a) 4062 74.54 19.712 0.6501 0.950

82.31 18.371 0.714 0.0971

X

lZ+ Cade (1967a) 4087.9 87.82 20.023 0.722 0.942

Exp 3735 13.87 0.971

HF

Xl£M- Cade and Huo(1367a) 4469 80.34 21.863 0.7693 0.397

Exp 4139.0 90.44 20.949 0.79; 0.917

X

lE+ Cade and Huo(1967a) 1187 14.71 4.766 0.1151 1.914

19.72 4.901 0.135 1.837

Molecule

and State

e

M.'.!1

5.859 0.1315 1.725

5.818 0.167 1.731

X

lZ+ Cade and Huo(1967a) 1741 26.86 6.394 0.1719 1.647

29.09 6.391 0.186 1.648

SiH

< 2 Il r Cade and Huo(1967a) 2144 30.91 7.558 0.1894 1.514

Exp 2042.5 35.67 7.498 0.214 1.521

Reference a

e

Ul X

e e MgH

Cade and Huo (1967a) 1598 21.7'

Exp 1495.7 31.5

Mil

Cade and Huo (1967a) 1741

Exp 1682.6

PH

Cade and Huo(1967a) 2515 36.37 8.664 0.2145 1.412

SII

2 X II Cade and Huo(1967a) 2860 42.32 9.756 0.2494 1.330

HC1

Cade and Huo(1967a) ,, D , ., ,- 3181 ^7.76 10.767 0.2682 1.264

75
Molecule

and State Reference w

e

HC1

x E ExP 2989.7 52.05 10.591 0.302 1.275

He +

X

2£+ Gi'bert and Wahl (1967b) 1790 7.42 1.1

He

2

Poshusta and Matsen(1963) 1743 91.7 6.6 0.26 1.13

.Scott et al (1966) 1665 43.4 6.739 0.216 1.12

K

u X

it

2

Das and Wahl (1966)H.F. 326

OVC 345

Exp 351

C

2

Fougere and Nesbet(1966) 1503

1538

1328

1527

Verhaegen et al (1967) 1970

1710

1730

2.78

2.69

2.67

1 .356

1 .394

1,.444

1..392

1,,255

1 .300

1 .306

Molecule

and State

X2£+ Cade et al (1966) 2570.5

2207.1

bV.+

-J

Cade et al (1966)

Exp

Cade et al (1966)

Exp

Cade et al (1966)

Exp

2„

A H Cade et al (1966) 2312.5

1902.8

3101.8

2419.8

9.809 2.065 0.0148 1.080

16.14 1.932 0.020 1.118

6.082 1.887 0.0155 1.129

14.91 1.740 0.018 1.176

19.88 2.296 0.0128 1.024

23.19 2.073 0.020 1.075

76
Molecule

and

State Reference

Cade et al (1966)

Exp

2729.6

2358.1

8.378 2.121 0.0135 1.065

14.188 1.999 0.0178 1.097

Wahl (1964)

Das and Wahl (1966) Das and Wahl (1967) Harris and Michels (1967) Exp

1257 9.85 1.003 0.0108 1.33

678 1.45 704 1.44 1072 16.44 0.9087 0.012 1.398

923.1 16.04 0.8938 0.022 1.409

Gilbert and Wahl (1967b) 510 0.50 1.9

A+

Gilbert and Wahl (1967b) 660 0.59 1.7

C1

2

Gilbert and Wahl (1967c) 577

Exp 559.7

2.2 0.24 0.0023 2.00

2.70 0.24407 0.00153 1.9878

Molecule

and State Reference ID x

e e

CI

X

2^ Gilbert and Wahl (1967b) 260 0.136 0.001 2.65

X

2^ Gilbert and Wahl (1967b) 3m 0.139 2.-

77
Mo lee nl

e

and State Reference

x'T''

HeLV

Schneiderman and Michels (1 965) 232.8 20.41 1.513 0.122 2.095

4

A

2 n

HeLi

Schneiderman and Michels (1965) 375.2

284 .

2

353.6

285.7

11.07 1.019 0.3043 2.553

5.32 0.724 0.0090 3.029

2.53 0.841 0.0086 2.810

39.68 1.722 0.133 1.964

xV McLean (196 4)

Exp

1134.5

964.1

9.441 1.580 0.0182 1.528

8.895 1.509 0.0241 1.564

xVLiNa

Bertoncini and Wahl (1967)H.F. 264

NO 256

2.94

2.90

Molecule

and

State Reference

S 1^ Matcha (1967)

Exp

671.5

641.0

4.671 0.704 0.0076 2.024

4.2 0.706 0.0080 2.021

x

1^

B

1^

A

x n

BeO

Yoshimine (1964)

Exp

Verhaegen and Richards

(1966)

1807 .

7

10.687 1.757 0.0151 1.290

1487.3 11.830 1.651 0.0190 1.331

1554 1.356

1409 1.403

1399 1.441

1372 1.436

Verhaegen et al (1967)

1 + V

x

3n

1790

2020

2070

1750

1.306

1.246

1.220

1.305

78
Molecule

and

State Reference

X

1 ^

Nesbet (1964a) 1413.8 9.9 1.495 1.272 Huo (1965 > 1*96 12.07 1.559 0.0185 1.246 Exp 1*02.1 11.8 1.510 0.016 1.265

CO

Mesbet (1964a) 2357.2

Huo (1965) 2431

Exp

NaF

2169.8

Matcha (1967) 588.3

Das and Wahl (1967) 590

Wahl et al (1967) 603

Exp 536.1

11.1 1.965 1.119

11.69 2.027 0.0153 1.101

13.295 1.931 0.0175 1.128

4.387 0.439 0.00468 1.920

1.93

1.93

3.83 0.437 0.00457 1.926

Molecule

and State Reference

e

NaCl

Matcha (1967) 378.3

Wahl and Gilbert (1967) 341

E>:p 364.6

X

1^ 2.589 0.215 0.00179 2.373

2.42

2.05 0.218 0.00162 2.360

Molecule

and Reference

J 1^

X

2!^

MgO

Richards et al (1966) 1055

887

856

880

8 18

ScO

Carlson et al (1965) 1329

1174

1318

1373

3cF

Carlson et al (1965) 97j

902

909

1.666

1.812

1.762

3 n 880 1.314

1 +

X £ 808 1.785

2„+

B £ Carlson et al (1965) 1329 1.678

1.625

1.654

1.615

1 A Carlson et al (1965) 970 1.801

1.751

1.806

79
Molecule

and

State Reference

d

1!^ Carlson and Moser(l%7) 1737 1.526

X

3A r 1731 1.542

H, Spectroscopic Constants

Reference

Coulson (1935) 3170

Christoffersen (1964) 3354 2790

Pearson et al (1966) 3610 4440

Calculated Geometry and Vibrational Frequencies

o H

2 H2

S NH3 P H- C H,4

SiH,4 N flt4

P H+

R

e

(A) 0.960 1.328 1.018 1.414 1.104 1.475 1.053 1.455 HXHe 106.39° 89.40° 109.16° 89.26 Tetrahedral Tetrahedral Tetrahedral Tetrahedral

^(Crn" 1

) 4411 3112 3672 2839 3709 2542 3634 2462

u>2 1364 985 645 902 1262 845

^3 4211 2798 3874 2791 3830 2557

WA 1035 864 1122 714

Menna et al (1966)

80
G. Dissociation Energies : Introduction

Hartree-Fock dissociation energies are obtained by substracting the atomic

H. F. energies from the molecular H.F. energy. Beyond Hartree-Fock dissociation energies are obtained relative to the natural limit for the procedure at hand. In the case of the valence extended Hartree-Fock or NO procedures, the asymptotic limit is again the H.F. atom

energies. For the VB calculations it is dependent on the basis set that is used.

Hydride Dissociation Energy

De (eV)

LiH

BeH

BH

CH

NH

OH

HF

NaH

MgH

A1H

SiH

PH

SH

HC1

Vr

X

Hartree-Focka

1.49

2.18

2.78

2.47

2.10

3.03

4.38

0.93

1.15

2.36

2.23

2.03

2.63

3.48

a. All Hartree-Fock results: Cade and Huo (1967a, b)

b. Bender and Davidson (1966)

c. Sanders and Krauss (1967)

d. Harris and Michels (1967)

Beyond H. F.

2.24b

, 2.36C

Exptl.

2.52

(2.6)

3.58

3.65

(3.8)

4.63

6.12

(2.3)

(2.3)

3.01

(3.32)

(3.34)

3.70

4.616

81
Homonuclear Dissociation Energy

Molecule Hartree-Fock

D

e (eV)Beyond Hartree-Fock Exptl.

Li

4

( 2jHg

8 X

1^g X2E+

X^"

g

b

1^S x

xr+ x^-

0.17c

0.89c

0.79c

5.18 f

3.13 f

3.59 f

1.28 c

-0.06c

-1.39c

-1.37 c

1.66a

1.65a

0.07 c

0.99"

5.39 e

0.95fo.41h ,2.01

1.1

6.36

9.90

8.86

7.73

5.21

4.23

3.57

1.69

0.74

Molecule

D

e (eV) Hartree-Fock Beyond Hartree-Fock Exptl

CI

2 ci ;

Ar+

2

g x2r+

0.87

1.28a

1.253

2.51

a. Gilbert and Wahl (1967a)

b. Reagan et al (1963)

c. LMSS (1967)

d. Das (1967)

e. Fougere and Nesbet (1966)

f. Cade et al (1966)

g. Das and Wahl (1967)

h. Harris and Michels (1967), the first number is for the Hartree-Fock basis while the second is obtained with a minimal Slater basis,

i. Gilbert and Wahl (1967c)

82
State

Heteropolar Dissociation Energy

Hartree-Fock Beyond Hartree-Fock Exptl.

LiO

LiF

LiNa

LiCl

BeO

BeF

BF

BO

CO

NO

NaF

NaCl

A2TT

a4 TI

2 r

X

1!^

x%+

xt+

x

2 ^

A: +

a

3

!!

x

2 n

r

x

1 ^

1.88»

4.07

C

0.05d

3.83 e

4.13 f

5.07 b

6.19 g

5.91 b

7.92 C

h 2.07

2.00 l

3.05

e

e 3.18

0.06"

0.89

0.41

0.45

0.65

3.7

4.84

4.7

8.58+0.5

S7.52

11.242

5.206

4.95

4.22

a. Schneiderman and Michels (1965)

b. LMSS (1967)

c. McLean and Yoshimine (1967)

d. Bertoncini and Wahl (1967)

e. Matcha (1967)

f. McLean and Yoshimine (1967)

g. Huo (1965)

h. Huo (1966)

i. Estimated from LMSS (1967) NO total energy and ground state atom energies of -129.21027 a.u.

j. Das and Wahl (1967)

83
H. Electron Affinities : Introduction

Ab initio calculation of electron affinities from beyond H. F. results is not possible today; direct calculation of the electron affinity of a molecule

by the difference in the H.F. energies of the ion and neutral molecule yields poor results. Systematic study of the homologous series of molecules and analyogous atoms does permit the estimation of the correlation energy and other properties of the ion. Cade (1967a, b) has completed such a program for the hydride

ions. The use of orbital energy from singlet symmetric ions is also illustrated. Note that other ions are listed in the orbital energy tables.

Electron Affinities of Molecules (eV)

Molecule EA(HF) -e EA(Corr) EA (Exptl.

)

CH

b 1.61 > 1.4

NH 0.22 >

OH -0.10 2.90 1.91 1.83

SiH 0.64 ~ 1.46

PH -0.23 ~0.93

SH 1.21 2.42 2.25 ~ 2.3

K0C 3.45 > 3.82d

2 _

a. Orbital with smallest energy for closed-shell ions.

b. Hydride results from Cade (1967a); (1967b).

c. Pfeiffer (Princeton) (1967).

d. Curran, R. K. (1962), Phys. Rev. 125, 910

84
I. Orbital Energies : Introduction

A variety of orbital energies are tabulated at the geometries listed

in Section B. The majority of diatomic results are for accurate H.F. calculations and are likely to be unchanged by future work. This can not be said for many of the polyatomic cases. Nonetheless, the orbital energies

tabulated here will provide the qualitative insight to the molecular shell structure and are presented to that purpose. Many molecules are missing from the following tables since the orbital

energies were presented with the potential energy curves in subsequent sections.

Hartree-Fock Oribital Energies

Homonuclear Diatomic

H, (V") Li,^) B,(V)

2 g

C (V")

2 8 2 8

3°8

40 „

0.5946 a 2.4523a

0.1816

7.7039"

0.7057

11.35983 15.6819b

1.0613 1.4736

0.6349

10

u 2a

u 30

u 40

u

IIIu in,

2.4520 7.7031

0.3636

0.3594

11.3575

0.5172

0.4579

15.6783

0.7780

0.6154

85
Orbital vV vV *A+/

&>'

108

2°8

3°g

4°g

5°g

20

u

30

u

in„

20.7296

1.6488

0.7357

20.7286

1.0987

0.7052

0.5319

20.2877

1.1865

0.3150

20.2871

0.7260

0.3062

0.08375

26.4207

1.8075

0.7823

26.4204

1.4763

0.8282

0.6507

40. 4763

2. 7957

1 .5179

.1698

40 .4763

2 .7956

1 .5160

1.5164

1.5162

a. LMS3 (1967)

b. Cade et al (1966)

Hartree-Fock Orbital Energies

Heteropolar Diatomic

Orbital cW uc( n )*

la 7.6336 11.1940

la 2.4508 2.4435

3a 0.4583 0.6218

4a 0.1978 0.2462

5a

6a

7a

in 0.2912

211

LiN(V) 3 Lio(2n

t

)

15.4463 20.4493

2.4344 2.4387

0.8203 1.0893

0.3031 0.4027

0.3774 0.4100

86
Hartree-Fock Orbital Energies

Heteropolar Diatomic

LiF (h+

) b LiNa (W

La

20

3cr

4a

5ff

60

70

8ff

9a

in

2n

311

4ti

ia

16.1114 40.4727

2.4286 2.7923

1.3817 2.4637

0.5046 1.5136

0.1783

0.4786 1.5129

,1C1 (W LiBr (T

04.7244 469.9253

10.4502 65.0563

7.9166 58.4110

2.4762 9.7284

0.9683 7.3362

0.4037 3.0691

2.4750

0.8918

0.3656

7.9164 58.4095

0.3759 7.3349

3.0675

0.3373

3.0700

Hartree-Fock Orbital Energies

Heteropolar Diatomic

IO

20

30

40

5CT

60

70

Be0( 1E+

) b BeF^rV

20.4514 26.2399

4.6994 4.7335

1.1580 1.5614

0.4649 0.6980

BeF(2n

r

) d

26.1924

4.7370

1.5251

0.6556

BOC2*^")"

20.5551

7.6796

1.3258

0.6315

0.5177

ITT

2TT

0.3943 0.3397 0.6275

0.1688

0.5197

87
BCf^r*)" BF (

1Z*) b cn ( 2 n )« co ( 1r

+

) b

la

20

3a

40

50

60

7<J

20.2287 26.3759

7.2777 7.7D79

1.0150 1.6977

0.3339 0.8533

0.0737 0.4044

15.6173 20.6643

11.3236 11.3597

1.2199 1.5210

0.5828 0.8038

0.5544

in

211

0.2179 0.5194

0.2429

0.6395

Orbital

CF(2 n ) a cs(4:+

) f worn )

e 1 + c

la

2a

3a

4a

5a

6a

7a

26.3744

11.3405

1.7081

0.9086

0.5480

91.9531

11.3434

9.0359

6.7117

1.1071

0.6921

0.4705

20.6911 40.4664

15.7179 26.0627

1.5939 2.7872

0.9257 1.5131

0.6802 1.3205

0.4395

in

2n

0.7449 6.6959

0.4634

0.6710 1.5107

0.4262

88
Orbital

10

20

30

40

50

6<T

70

80

90

100

110

in

211

3ir

4tt

1 + c NaCl( £ ) 1„+ <= NaBr( Z )

104.6965 489.9002

40.4996 65.0351

10.4216 58.3893

7.8881 40.4971

2.8191 9.7068

1.5418 7.3145

0.9354 3.0485

0.3639 2.8165

1.5374

0.8643

0.3315

7.8879 58.3877

1.5419 7.3128

0.3474 3.0468

1.5383

0.3141

1 + b MgO( Z )

1 + b A1F( Z )

49.0580 58.4962

20.4374 26.2456

3.7949 4.9067

2.3092 3.2166

1.0785 1.5344

0.3177 0.6756

0.3365

2.3112

0.3496

3.2158

0.6157

0.3049

Orbital

la

20-

30

4CT

SO

60

70

8CT

9CT

in

2n

311

SiO( 1£+

) b

4.2551

0.4864

nh+

) ,+,b

68.8027 79.9725

20.5239 15.5855

6.1539 7.5238

4.2559 5.4161

1.2787 1.1597

0.6103 0.6481

0.4345 0.4844

5.4146

0.4574

ClF^r4") 8

8.1174

0.7237

0.4908

KF ( W

104.9343 133.4936

26.3673 26.0335

10.6541 14.4498

8.1220 11.4796

1.6347 1.7108

1.1020 1.3047

0.7011 0.9103

0.4090

11.4797

0.9211

0.4010

89
la10

yo

4a

5a

6a

70

8a

9a

10a

lia

ITT

211

sn

16

1 + c Kacr

)

133.5253

104.6734

14.4822

11.5124

10.3995

7.8649

1.7436

0.9650

0.8990

0.3372

CaO(V)b

149.2651

20.3183

16.7186

13.5279

2.1479

1.2834

0.9525

0.2653

.1.5126 13.5270

7.8648 1.2556

0.9528 J. 2617

0.3281

Z + c RbF( 2 ) SrOcW

551.4045 583.6000

74.9900 80.2804

67.8463 72.8900

26.0271 20.3036

12.0819 13.3588

9.4361 10.5848

4.6733 5.5703

1.4808 1.7823

1.2962 1.1006

0.7634 0.8648

0.3974 0.2487

67.8458 72.8891

9.4367 10.5857

4.6753 5.5695

0.7737 0.9993

. 3964 0.2491

4.6759 5.5695

a. LMSS (1967)

b. McLean and Yoshimine (1967)

c. Matcha (1967)

d. Walker and Richards (1967)

e. Verhaegen and Richards (1967)

f. -Richards (1967)

g. Stevens (1967)

Hartree-Fock Orbital Energies linear Triatoraic

Orbital

-s

LiOH( 1£+

) a (FHF)"(1Z+) b,c

c

3 (^)c ' d

( OCN )" (W

10 20.4042 25.9331 11.2504 20.3177

20 2.4381 25.9331 11.2502 15.2657

3a 1.1644 1.2505 1.1630 11.0716

40 0.5470 1.1961 0.8673 1.1851

50 0.4676 1.0377 0.9063

60 0.2717 0.4324 0.4694

70 0.4777 0.2928

lit 0.3701 0.3165 0.4016 0.3675

211 0.2864 0.1349

90
Orbital

-s

FCN(V") b (SCN) "(V)b ClCN(1£

+

) b co

i

(

1£j)b ' e

10 26.4410 91.7031 104.9336 20.6492

20 15.6113 15.3121 15.6063 20.6493

30 11.3988 11.0670 11.3479 11.4601

40 1.7701 8.7079 10.6579 14.7698

50 1.2536 6.3903 8.1244 1.5299

60 0.9331 0.9503 1.2717 0.7434

70 0.6020 0.7823 1.1949 0.8002

80 0.3903 0.7570

90 0.3059 0.5884

III 0.8182

2n 0.5004

311

6.3872

0.2785

0.1124

8.1218

0.5983

0.4646

0.7149

0.5443

Orbital BeF^1!*) '" sco ( 1r

+

) b N" (^)c - f Li,0 (lr+)«.3

10 26.1833

20 26.1829

30 4.7709

40 1.5310

50 1.5246

60 0.6531

70 0.6448

80

90

91.9960

20.6575

11.4411

8.9991

6.6805

1.5026

1.0941

0.7796

0.6386

15.4687

15.2198

15.2200

0.9674

1.1950

0.2810

0.3505

20.3398

2.3625

2.3627

0.3260

1.0080

in 0.6275

2fT 0.5982

3n

6.6777

0.6561

0.4226

0.3991 0.2655

a. Ritchie and King (1967b)

b. McLean and Yoshimine (1967)

c. Orbitals are alternately gerade and ungerade for (J and vice versa for IT.

d. Clementi and McLean (1962a)

e. Peyerimhoff et al (1967)

f. Peyerimhoff and Buenker (1967)

g. Buenker and Peyerimhoff (1966)

91
Hartree-Fock Orbital Energies

Non-linear Triatomic

Orbital FOH^A ) a N0

2 ~( 1 A

1

) b

la 26.3435 20.2663

2a 20.6866 15.4767

3a 1.6751 1.2922

4a 1.3239 0.5764

5a 0.7864 0.4181

6a 0.6925 0.1495

7a 0.6039 0.1267

°3 ( V F

2 CAj}

20.8896 26.3833

20.7255 20.8043

1.7233 1.7760

1.1108 1 . 2860

0.8168 0.8084

0.5657 0.7268

0.4906 0.6522

lb 0.7353

2b 0.5484

3b

4b

5b

6b

20.2666

1.0594

0.3811

0.3797

0.1838

a. Buenker and Peyerimhoff (1966)

b. Pfeiffer (1967)

c. Peyerimhoff and Buenker (1967)

20.7255

1.4263

0.7808

0.7602

0.5807

Hartree-Fock Orbital Energies, AH

26.3833

1.6443

0.8273

0.7945

0.6811

0.5887

BHjVa^3 CH

2

(1A

1

) b NH"(lA

l

) c H

2 (1A

:

)

C H

2 S (U^6

la 7.3903 11.3120

2a 0.4481 0.9095

3a 0.00213 0.3859

4a

5a

lb - 0.2957 0.5712

15.1656

0.7335

0.0913

0.2727

2b.

0.5624 92.4785

1.3615 9.0798

0.5737 6.6350

0.9403

0.4543

0.7273 6.6362

0.5307

lb

2b,

a. Geller et al (1967)

b. Krauss (1964)

c. Ritchie and King (1967b)

d. Ritchie and King (1967a)

e. Moccia (1964c)

0.0205 0.5046 6.6318

0.3506

92
Hartree-Fock Orbital Energies

Linear Tetratomics

HCCH( 1I^) a HCCH( 1 £

f

) b g NCCM(1t+) £

10

g 11.2440

2a

8 1.0296

3G

g 0.6828

4°g

5°g

iqi 11.2403

20 u 0.7698

3<h

4q,

u 0.4103

^.

11.2585

1.0406

0.6835

11.2548

0.7658

0.4131

a. McLean and Yoshimine (1967)

b. Buenker et al (1967)

15 .6576

1 1 .3554

1 3048

9868

6279

15 6576

11 3543

1 2797

6438

0.6035

0.5004

Hartree-Fock Orbital Energies

Linear Tetratomics

Orbital

LiCCH( 1i:+)

10 11.1454

20 11.1250

30 2.4519

4o 0.9404

50 0.6596

60 0.4207

70

8o

90

in 0.32/0

2n

FCCH (!£<-)

26 .3837

11 3410

1 1 2470

I 7071

1 0529

8632

7281

0.7617

0.4196

C1CCH (!£+-)

10, .8889

11 .2984

11 .2495

10 .6136

8 .0802

1 1941

1 0198

7513

6722

8 0778

5503

3919

McLean and Yoshimine (1967)

93
Orbital

la

1 4.4740

2a

t 0.2808

3a

1

BeHjVAj)15 BH

3

( : A{) b CH3 ( 2AJ') C CHj ( l A[) d

7.6173 11.2041 10.8872

0.6943 0.9155 0.6153

0.3723 -0.0077

0.1530 0.4833 0.5834 0.2717

Orbital

NH3 C^)6 FH

3

(*A

L

) f

la 15.4876

2a 1.1935

3a 0.3859

4a

5a

le 0.5967

2e

80.1650

7.4798

5.2572

0.8380

0.3671

5.2587

0.4778

a. Both C, and D-, symmetries are represented; for the D-, orbitals the appropriate primes must be added.

b. Peyerimhoff et al (1966)

c. Hackmeyer and Whitten (1967)

d. Kari and Csizmadia (1967b)

e. Rajagopal (1965)

f. Moccia (1964b)

Hartree-Fock Orbital Energies, AH

4

BH "(XA ) a CH ( L A ) b

4 1 4 1

la

l 7.2676

2a

l 0.4434

lt

2 0.1765

11.2216

0.9295

0.5348

a. Krauss (1964)

b. Ritchie and King (1967a)

94
J. Energy and Properties as a Function of the Interauclear Distance: Introduction

Results are presented for a series of diatomic molecules calculated to high accuracy in the H. F. approximation. These studies were carried out at the IBM laboratory at San Jose but similar results or capability exist at other laboratories (e.g. LMSS or Argonne). Since these results were

available they are presented as a witness to one area of calculational

capability.

Units: |J 10 esu cm, 9 10 esu cm , q 10 esu/cm ,

-5 2 X 10 erg /gauss mole

iF ( lO2 20 2 30 2 4C2

1114

, 1£+ LiF )

R -E n e q

i q

2 X

I

2.45 106.9569 5.277 4.229 -0.040 -2.879 -2.061

2.65 106.9819 5.742 4.921 -0.094 -1.894 -2.208

2.7877 106.9894 6.062 5.408 -0.112 -1.291 -2.316

2.8377 a 106.9916 6.295 5.769 -0.118 -0.869 -2.397

2.9877 106.9916 6.529 6.138 -0.121 -0.536 -2.481

3.20 106.9869 7.033 6.950 -0.118 0.115 -2.669

3.55 106.9713 7.885 8.384 -0.102 0.337 -3.003

a. -e : 26.1114, 2.4286, 1.3817, 0.5046, 0.4786

McLean and Yoshimine (1967)

95
LiCl ( lo 2 - 6o 2 Hi4 2li4

, llf )

-E

3.35 467.0387 6.167

3.60 467.0517 6.709

3.66 467.0531 6.843

3.723 467.0541 6.984

3.825 b 467.0547 7.218

3.91 467.0543 7.415

A. 00 467.0533 7.626

4.10 467.0515 7.864

4.55 467.0381 8.966

-0.0574

-0.0679

-0.0700

-0.0719

-0.514

0.389

0.687

1.271

a. Mv = 7.218+0.0753 (v+1/2) + 0.0002 (y+1/2) 2

;

Mv (exp) = 7.0853 + 0.0864 (v+1/2) + 0.0006 (v+l/2) ;

b. -e : 104.7244, 10.4502, 7.9166, 2.4762,

0.9683, 0.4037, 7.9164, 0.3759.

Matcha (1967)

BeO ( ia 2 2CT2 3a 2 4a 2 inA

> 1Z+)

R -E H e q

l q2 XL

1.80 89.18098 5.745 3.476 -6.395 0.489 -2.030

2.10 89.39983 6.508 4.838 -5.101 -0.001 -2.313

2.35 89.45122 7.138 5.562 -3.478 -0.140 -2.570

2.4377 a 89.4541" 7.353 6.354 -2.824 -0.161 -2.665

2.50 89.45299 7.502 6.631 -2.329 -0.170 -2.734

2.75 89.43088 8.037 7.693 0.019 -0.173 -3.020

3.10 89.37967 8.223 8.649 5.523 -0.124 -3.473

3.80 89.30961 5.380 7.110 17.81 -0.024 -4.737

5.50 89.26894 1.430 4.360 24.43 0.005 -3.489

a. -e : 20.4514, 4.6994, 1.1580, 0.4649, 0.3943

McLean and Yoshiraine (1967)

96
BI- ( ia 2 ->5o 2 1

II4

) J £+)

R -S U e q

l q2 yL

" 2.00 124.1090 -1.931 -4.312 -1.791 -1.139 -3.077

2.10 124.1413 -1.689 -4.393 -1.834 -0.235 -3.192

2.1925 124.1582 -1.448 -4.447 -1.835 0.498 -3.301

2.391 s 124.1671 -0.883 -4.482 -1.755 1.980 -3.541

2.5775 124.1559 -0.293 -4.401 -1.624 3.108 -3.775

2.77 124.1352 0.371 -4.193 -1.463 4.005 -4.027

2.9625 124.1107 1.083 -3.855 -1.297 4.653 -4.289

a. -6 : 26.3759, 7.7079, 1.6977, 0.8533, 0.4044, 0.7444

McLean and Yosiiiwine (1967)

CO ( ia 2->5a 2

lll'*, 1

i:+

)

R -E M e q

i q

2 X

L

1.30 112.7025 -0.546 -2.563 -3.574 -4.456 -2.740

1.898 112.7576 -0.319 -2.468 -3.721 -3.887 -2.859

2.015 112.7869 -0.029 -2.343 -3.798 -3.141 -3.007

2.132 3 112.7891 0.280 -2.204 -3.808 -2.348 -3.159

2.249 112.7733 0.602 -2.048 -3.778 -1.522 -3.316

2.366 112.7461 0.934 -1.876 -3.729 -0.666 -3.479

2.483 112.7119 1.271 -1.690 -3.679 0.226 -3.647

a. -e : 20.6643, 11.3597, 1.5210, 0.8038, 0.5544, 0.6395

McLean and Yoshimine (1967)

97
NaF ( la 2-* 6a2

ill 4

2ll4

> 1 Z

f

)

-E

3.10 261.3503 7.222

3.36 261.3728 7.754

3.50 261.3773 8.051

3.56 261.3782 8.180

3.628 b 8.35

3.71 261.3781 8.510

3.7794 261.3773 8.510

3.90 261.3750 8.941

4.35 261.3603 10.02

-1.334 -0.538

-1.249 -0.355

-1.158 -0.155

-1.088 -0.0044

a. MV= 8.337 + 0.610 (v+1/2) + 0.002 (vfl/2) 2

;

Mv (exp) = 8.1235 + 0.0644 (v+1/2) + 0.0004 (v+l/2) :

b. -e : 40.4665, 26.0627, 2.7872, 1.5131, 1.3205,

0.4395, 1.5107, 0.4262

Matcha (1967)

2 2 4 „4 1 +

NaCl ( 10-* 80 in 311, £ )

3.70 621.4167 7.603

4.15 621.4521 8.444

4.30 621.4559 8.754

4.40 621.4571 8.968

4.4609 621.4574 9.101

4.485 b 621.4574 9.101

4.60 621.4570 9.412

4.75 621.4553 9.758

5.00 621.4505 10.356

-1.025

-0.919

-0.805

-0.743

-0.263

0.187

0.680

0.953

a. HV= 9.154 + 0.0580 ( v + 1/2 ) + 0.0003 ( v 1/2 ) Z

;

Mv (exp)= 8.9734 + 0.0570 (v+1/2) + 0.0005 (v+1/2)

b. -e : 104.6965, 40.49So : 10.4216, 7.881, 2.8191,

1.5418, 0.0354, 0.3639; 7.8879, 1.5419, 0.3474

Matcha (1967)

98
4 U+x

MgO ( la - 6cT in

4 2n *, V)

q q X

1 2 L

2.50 274.2087 8.217 0.681 -0.746 0.379 -4.731

3.00 274.3653 9.250 0.361 -0.756 2.545 -5.808

3.20 274.3754 9.082 0.315 -0.594 4.859 -6.317

3.3052 a 274.3751 8.842 0.221 -0.517 6.321 -6.603

3.40 274.3732 8.580 0.118 -0.458 7.666 -6.867

3.60 274.3653 7.868 -0.093 -0.359 10.50 -7.456

4.10 274.3405 6.041 -0.217 -0.209 16.04 -9.050

5.10 274.3073 3.512 -0.662 -0.072 21.50 -12.70

a. -e : -49.0580, -20.4374, -3.7949, -2.3092,

-1.0785, -0.3177, -2.3112, -0.3496.

McLean and Yoshimine (1967)

A1F ( la2 - 70 2 in4 2^ , lE+)

R -E U e q

i S

X

I,

2.60 341.4127 -0.030 - 5 . 944 -6.415 -2.312 -5.938

2.85 341.4687 0.568 -6.322 -4 . 994 -0.843 -6.535

3.05 341.4824 1.114 -6.608 -4.141 0.133 -7.045

3.126 3 341.4832 1.337 -6.713 -3.867 0.456 -7.247

3.25 341.4811 1.717 -6.876 -3.465 . 928 -7.586

3.45 341.4718 2.369 -7.126 -2.920 1.551 -8.157

3.70 341.4544 3.240 -7.418 -2.375 2.116 -8.917

a. -e : -58.4962, -26.2456, -4.9067, -3.2166,

-1.5344, -0.6756, -0.3365, -3.2158, -0.6156

McLean and Yoshimine (1967)

99
2 2 4 4 1 +

SiO ( 1C7 - 70, lH 2ll , £ )

R -E H e 1

1 q

2 XL

2.304 363.6988 2.280 -5.123 -10.97 -5.082 -5.149

2.50 363.8035 2.745 -5.124 -9.427 -4.249 -5.574

2.604 363.8365 3.010 -5.153 -8.752 -3.748 -5.812

2.75a 363.8523 3.397 -5.219 -7.952 -3.006 -6.160

2.854 363.8516 3.681 -5.282 -7.473 -2.458 -6.419

3.104 363.8250 4.378 -5.484 -6.584 -1.085 -7.075

3.404 363.7693 5.204 -5.831 -5.'945 0.732 -7.925

a. -e : -68.8027, -20.5239, -6.1539, -4.2559,

-1.2787, -0.6103, -0.4345, -4.2551, -0.4864

McLean and Yoshimine (1967)

PN ( 1a2 - 70 2 in4

211 4

, V")

R -E M G q

i S

X

L

2.268 395.0243 3.238 -3.803 -11.66 -5.376 -5.053

2.45 395.1376 3.246 -3.338 -9.758 -5.270 -5.437

2.568 395.1725 3.244 -3.055 -S.677 -5.116 -5.699

2.67

a 395.1857 3.241 -2.818 -7.828 -4.953 -5.932

2.818 395.1848 3.232 -2.487 -6.720 -4.686 -6.283

3.068 395.1497 3.211 -1.958 -5.112 -4.204 -6.903

3.368 395.0800 3.178 -1.375 -3.477 -3.670 -7.705

a. -e : -79.9725, -15.5855, -7.5238, -5.4161, -1.1597,

-0.6481, -0.4844, -5.4146, -0.4574

McLean and Yoshimine (1967)

100
CaO ( la 2 - 8a2

ill4 - 3ll4

, V")

R -E H 9 q

1 q 2 XL

2.9912 751.4896 9.366 -7.667 -0.452 -1.306 -7.602

3.1412 751.5243 10.022 -7.596 -0.817 -1.646 -8.050

3.2912 751.5415 10.552 -7.557 -0.909 -1.686 -8.523

3.4412s 751.5478 10.946 -7.578 -0.846 -1.432 -9.023

3.6412 751.5435 11.203 -7.756 -0.628 -0.530 -9.737

3.8912 751.5264 10.652 -8.384 -0.264 2.346 -10.74

4.1412 751.5065 8.241 -8.692 -0.219 2.292 -11.95

a. -e : -149.2651, -20.3183, -16.7186, -13.5279, -2.1479,

-1.2834, -0.9525, -0.2653, -13.5270, -1.2556, -0.2617

McLean and Yoshimine (1967)

SrO ( io* - no2 in4 - 5fi4i 6 4

, 1r

f

)

R -E M 9 q

i q2 XL

3.10 3206.1729 7.643 -12.46 2.372 0.715 -9.820

3.25 3206.2059 8.439 -13.01 0.878 -0.150 -10.36

3.40 3206.2242 9.185 -U.52 -0.055 -0.840 -10.94

3.525 3206.2306 9.763 -13.93 -0.598 -1.263 -11.44

3.6283a 3206.2311 10.207 -14.24 -0.805 -1.500 -11.87

3.78 3206.2262 10.798 -14.68 -0.911 -1.638 -12.52

4.10 3206.2007 11.663 -15.55 -0.618 -0.727 -14.02

a. -s : 583.6000, 80.2804, 72.8900, 20.3036, 13.3588,

.10.5848, 5.5703, 1.7823, 1.1006, 0.8649, 0.2487,

72.8891, 10.5857, 5.5695, 0.9993, 0.2491, 5.5695.

McLean and Yoshimine (1967)

101
K. Potential Energy Curves : Introduction

Examples of accurate H. F. , extended H. F. , adC, and VB techniques are tabulated below. Both distances and energies are given in atomic units.

In a number of instances figures were lifted from the original papers to illustrate the different techniques. A very few polyatomic curves are included. The VB calculation of BeH2

and the diatomic VB calculations show proper asymptotic dependence. Since

they have also been used to obtain a number of the excited states it was felt

that the VB calculations should be included even when more accurate surfaces may exist for a given state as in He2 . Hartree-Fock results are included near equilibrium for stable polyatomic

species including the orbital energies. One example of a reaction surface is included which also exhibits proper asymptotic dependence even though it is an approximate H.F. calculation. In this section both R and E are in atomic units.

Potential Energy Curves of Hydrogen

State

X

1 ^g

> 3x+ s 1* -M

1.0 -1.1245385 -0.6215227

1.5 -1.1723537 -0.8096095

2.0 -1.1381312 -0.8970636

2.5 -1.0939273 -0.9454463

3.0 -1.0573118 -0.9720104

4.0 -1.0163689 -0.9933781

5.0 -1.0037626 -0.9986849

6.0 -1.0008150 -0.9998125

CO -1.0 -1.0

-0.5812963

-0.7200327

-0.7520541

-0.7524996

-0.7354677

-0.7147955

-0.6948364

-0.625

-0.5724911

-0.7004638

-0.7182230

-0.7071783

-0.6892372

-0.6566106

-0.6369889

-0.6283423

-0.625

X~i/ , b"^" , C'll : Kolos and Wolniewicz (1965c)

g u' u

f 1 ^, b

3^. c^

S

B 2T": Kolos and Wolniewicz (1966a)

102
Potential Energy Curves of HeH

R Hartree-Fock

1.2 -2.917390

1.4 -2.932594

1.6 -2.930450

1.8 -2.921683

2.5 -2.888782

3.5 -2.868619

4.5 -2.863752

CO -2.8616799

Correlated

2.9620088

-2.9779726

•2.9762475

-2.9675157

iE

0.044619

0.045379

0.045797

0.045833

-2.9037244 0.0420445

a. Peyerimhoff (1965)

b. Wolniewicz (1965)

Energy As A Function of the Internuclear Distance

HeH

E ( X

2!*) E ( 2n ) E (V)

1.0

1.25

1.5

2.0

3.0

4.0

6.0

10.0

-3.00243

-3.06456

-3.06983

-3.04399

-3.01159

-3.00382

-3.00112

-3.00243

-3.06456

-3.06983

-3.04399

-3.01159

-3.00382

-3.00112

-3.02196

-3.08194

-3.08304

-3.04801

-3.01045

-3.00321

-3.00082

Michels and Harris (1963)

103
Energy As A Function of tie Internuclear Distance

LiH ( 10 2 20 2

, 1£+

) BeH( IT 2 20 2 30 , 2tf )

R -E

2.00 7.91322 15.11955

2.20 7.94594 15.14217

2.40 7.96663 15.15170

2.528b 15.15313

2.60 7.97887 15.15274

2.80 7.98517 15.14832

3.015 3 7.98731

3.00 15.14045

3.20 7.98646

3.30 15.12496

3.60 7.97932

3.70 15.10139

4.00 7.96824 15.08338

a. LiH, -e : 2.4452, 0.3017

b. BeH, -6 : 4.7064, 0.4732, 0.3126

Cade and Huo (19674) 2221+ 2 2 2 n 2„ BH ( IO 2D 3<J , E ) CH( 10 2C 30 ill, IT )

1.60

1.70 25.05933

2.00 25.11803

2.086b

2.20 25.13016

2.305a 25.13147

2.40 25.13056

2.60 25.12408

2.70

2.90 25.10763

3.20 25.03779

3.50 25.06724

a. BH, - e : 7.6842

b. CH, -e : 11.3135

38.21353

38.24259

38.27826

38.27 958

38.27767

38.26755

38.24395

38.17233

11.3135, 0.8349, 0.4563, 0.4145 Cade and Huo (1967a>

104
Energy As A Function of the Internuclear Distance

NH ( lO 2 2a 2 30 2 HI2

, h') OH ( 10 2 20 2 30 2 iH3

, ^i)

1.40 75.34382

1.45 54.88846

1.50 75.38378

1.55 54.92947

1.70 54.96392 75.41829

1.795

b 75.42127

1.90 54.97826 75.41837

1.9233 54.97838

2.10 54.97254 75.40163

2.30 54.95667

2.40 75.363o7

2.60 54.92492 75.33582

2.80 75.30822

3.00 54.87971

a. NH, -e : 15.6082, 1.0480, 0.5535, 0.5377

b. OH, -e : 20.6165, 1.3138, 0.6662, 0.5731

Cade ="H Huo (1967^

HF ( 1CT 2 20"2 3C 2 in\ LE

+

)

K -E

I . 325 99. 93545

1 ,37 100..01003

1 ,427 ;.oo, 03280

1 .50 100..05254

1 ,65 100.,06996

1 ,596

a

loo..07077

L .?,3 1 00 ,06731

1 .933 100 .05540

2 .10 100 .03357

2 .243 100 .01183

2 .40 99 . 93676

a. -6 : 26.2939. 1.60)9, 0.7759, 0.6521

Cade and Huo (1967a) 105
Energy As A Function of the Internuclear Distance

NaH ( 10 2 - 40 2 in4

, V ) MgH( 102- 402 50 in 4, 2i+)

-E

2.00 162.,2012

2.20 162,,2651

2.50 162,,3285

2.75 162 ,3601

2.80

3.00 162 .3788

3.10

3.20 162 .3872

3.259b

3.40 162 .3915

3.566 a 162,.3928

3.70 162 .3927

3.80

4.15

4.25 162 .3854

4.50

5.00 162 .3675

199.9699

200.0448

200.1112

200.1433

200.1553

200.1566

200.1557

200.1467

200.1344

200.1206

a. NaH, -e : 40.4662, 2.7869, 1.5077, 0.2752, 1.5090

b. MgH, -e : 49.0450, 3.7818, 2.2988, 0.3909, 0.2594, 2.3005

Cade and Huo (1967^

106
Energy As A Function of the Internuclear Distance

A1H( la 2 - 50 2 in 4

, ltf ) siH( la2 - 5a 2 in4 2TT, 2Tl )

-E

289.3033

239.3715

289.4099

289.4290

289.4362

289.4347

289.4286

289.4194

289.4085

289.3845

58.4894, 4.8999, 3.2082, 0.4966, 0.2883, 3.2090

b. SiH, -e : 68.8064, 6.1512, 4.2514 0.6299, 0.3776,

4.2520

2.00 242.2913

2.20 242.3671

2.40 242.4141

2.60 242.4418

2.80 242.4565

2.861 b

3.00 242.4627

3.113a 242.4634

3.20 242.4630

3.40 242.4597

3.60

3.80 242.4465

4.00

4.20 242.4296

4.60 242.4119

a. A1H, -e : 58.48'

Cade and Huo (1967t)

107
Energy As A Function of the Internuclear Distance

PH( la2 - 5a2 in* 2H2

, %" ) SH( la 2 - 5a 2 in* 2fl3, 2ni>

R -E

1.80 341.0922 397.9439

2.00 341.1970 398.0360

2.10 341.2304 398.0633

2.20 341.2546 398.0818

2.40 341.2828 39S.0996

2.512 398.1017

2.60 341.2928

2.668a 341.2934

2.70 398.0972

2.80 341.2916

3.20 341.2715 398.0604

3.40 341.2573 398.0418

3.60 341.2420 398.0229

a. PH, -e : 79.9631 . 7 .5050 , 5 .3961, .7738, .4583, 5.3960, 0.3785

b. SH, -e : 91.9840 . 8,,9855,, 6. 6657. 0..9411, 0. 5444, 6.6645,, 0.4122

Cade an d Huo (1967u»

Energy As A Function of the Internuclear Distance

HC 1 ( 1CT 2 - 50 2

III4 2U4

, 1Z+

)

R -E

1.80 459.9902

1.90 460.0365

2.00 460.0685

2.10 460.0896

2.20 460.1024

2.389a 460.1104

2.50 460.1083

2.80 460.0884

3.00 460.0689

3.20 460.0475

3.60 460.0040

a. -S : 104.8479, 10.5739, 8.0417, 1.1188, 0.628^- 8.0391, 0.4765

Cade and Huo (1967&)

108
Energy As A Function, of the Internuclear Distance HeH+(la2

2ct 2 3a 2 lnA

, ^

R

1.35

1.5

1.6

1.7

1.8 1.83*

1.9 2.0

2.1

2.2 2.4

2.7 3.0

3.5 4.0 4.5

-128.53942

-128.59568 -128.61469

-128.62448 -128.62812

-128.62836 -128.62773

-128.62479

-128.62026 -128.61492

-128.60330

-128.58728 -128.57470

-128.56128 -128.55418

-128.55089

a. Orbital energies! -33.3381,-2.49750,-1.45857,-1.38468.

Peyerimhoff (1965)

Potential Energy Curves of He +

u h+* 2^* 2£+*** 2J+*

0.5 2.2926 1.8737

0.75 3.9033 3.3448

1.0 4.5001 3.8088

1.25 4.7736 3.9256

1.5 4.9014 3.9118

2.0 4.9701 3.9068

2.05 4.9706 3.9089

3.0 4.9356 4.0124

4.0 4.9056 4.0944

5.0 4.8940 4.1488

6.0 4.8902 4.1768

10.0 4.8884 9 4.1876

12.0 4.88846 4 . 1806

1 . 3044

2.9825

3.4912

3.6355

3.6653

3.8281

3.8431

3.9667

4.0317

4.0730

4.0986

4.1471

4.1549

0.4765 -0.6339

1.9891 1.6240

2.6971 2.5863

3.2412 2.9834

3.5470 3.J426

3.6902 3.6817

3.7037 3.6916

3.9259 3.7568

4.0201 3.8382

4.0575 3.9181

4.0779 3.9833

4.1119 4.0964

4.1198 4.1105

Michels (1967)

109
-E

2T+ 2Z+

* 2~'r** 2^ 2j+i

0.5 2.1552 1.9677

0.75 3.6223 3.3267

1.0 4.0108 3.6906

1.25 4.0779 3.7814

1.5 4.1818 4.0451

2.0 4.5828 3.9912

2.05 4.6065 3.9895

3.0 4.8214 4.0447

4.0 4.8713 4.1282

5.0 4.8839 4.1760

6.0 4.8874 4.1969

8.0 4.8885 4.2042

10.0 4.8886 4.1970

12.0 4.8885 4.1881

Michels (1967)

3.7506

3.8081

3.8149

3.8498

4.0285

4.0682

4.0914

4.1180

4.1332

4.1419

1.0703

2.0920

3.0705

3.7144

3.7013

3.7496

3.7673

3.9439

4.0173

4.0546

4.0771

4.1022

4.1162

4.1249

-0.6868

1.3464

2.4336

3.0621

3.4179

3.6161

3.6209

3.7513

3.8283

3.9022

3.9659

4.0499

4.0895

4.1061

2 *

n

g u

2 *

n

0.5 2.0411

0.75 3.3222

1.0 3.7037

1.2 3.8054

1.5 3.8392

1.75 3.8361

2.0 3.8735

3.0 4.0449

4.0 4.0943

5.0 4.1142

6.0 4.1227

8.0 4.1277

10.0 4.1278

12.0 4.1276

2.0411

3.0208

3.4048

3.5080

3.5860

3.7561

3.8295

3.907 9

3.9882

4.0370

4.0672

4.0992

4.1132

4.1190

2.3282

3.6096

3.9775

4.0636

4.0751

4.0560

4.0413

4.0683

4.1053

4.1218

4.1287

4.1322

4.1314

4.1303

1.9999

3.2905

3.6660

3.7546

3.7743

3.7725

3.7782

3.8933

3.9798

4.0289

4.0595

4.0928

4.1080

4.1152

Michels (1967)

110
Energy As A Function of the Internuclear Distance

Li , xV"1 2> L

i E(SCF) E(ODC) E(OVC)

4.0

4.5

4.75

4.77

5.0

5.25

5.37

5.5

6.0

8.0

12.0

-14.852990

•14.869718

14.871796

•14.871484

14.868655

•14.859537

14.873465

• 14.877403

14.879630

•14.881261

-14. 881046

-14.871553

-14.865660

-14.884424

-14.895621

-14.898108

-14.898849

-14.898876

-14.893667

-14.877459

•14.866116

a. ODC- Optimized Double Configurations.

b. OVC- Optimized Valence Configurations.

Energy As A Function of Internuclear Distance

N 2 (la

g

2 lau

2 2a

g

2 2au2 3j

g

2

1ttu

4

. X

1^)

: 2a 2a 3ct

1.65 108.7887

1.82 108.9489

1.85 108.9635

1.905 108.9825

1.95 108.9914

2.0132 108.9956

2.05 108.9944

2.068 108.9928

2.0741 108.9922

2.09 108.9904

2.15 108.9799

2.20 108.9679

2.292 108.9397

2.34 108.9226

2.45 108.8792

2.90 108.6828

Cade et al (1966)

1.6292 0.7002 0.6534 0.7355

1.5699 0.7331 0.6459 0.6798 1.5584 0.7387 0.6459 0.6709

1.5372 0.7489 0.6422 0.6558 1.5194 0.7570 0.6401 0.6438

1.4953 0.7687 0.6379 0.6285

1.4803 0.7747 0.6355 0.6194

1.4736 0.7780 0.6350 0.6154

1.4712 0.7790 0.6346 0.6140

1.4651 0.7818 0.6338 0.6106

1.4421 0.7918 0.6306 0.5974

1.4235 0.8001 0.6280 0.5872

1.3902 0.8149 0.6226 0.5693

1.3736 0.8224 0.6196 0.5606

1.3376 0.8393 0.6123 0.5418

1.2217 0.9009 0.5759 0.4824

111
Potential Energy of F

1.8

2.2

2.68

3.0

3.5

6.0

Hartree-Fock

98.41814

98.73236

98.76825

98.73302

98.66024

98.45753

-E

0VC a 198 .44543

198 .77720

198 .84853

198 84551

198 83094

198 81799

198 81784

Extended Hartree-Fock (OVC) 0VCb 198.45263

198.85464

198.83589

198.81799

198.81784

a. Correlate only 30

b. Additional 20 ,

into 30

u Das and Wahl (1967)

2o

u

, 30 , mu , in excitations

Potential Energy of F r

v- V

2.68

3.2

3.6

4.0

4.4

4.8

5.2

5.6

6.0

6.6

7.2

0.0346

-0.0516

-0.0609

-0.0552

-0.0457

-0.0365

-0.0288

-0.0227

-0.0179

-0.0129

-0.0096

a. Hartree-Fock

Gilbert and Wahl (1967c)

0.0673 0.1529

0.0209 0.0751

0.0037 0.0386

0.2027

0.1132

0.0662

112
Potential Energy of Ne^

2.5 0.0290

2.8 -0.0417

3.0 -0.0574 0.0439 0.1174 0.1961

3.2 -0.0607 0.0232 0.0736 0.1398

3.5 -0.0549 0.0049 0.0367 0.0863

4.0 -0.0378

5.0 -0.0143

c*9 ')

a. Hartree-Fock

Gilbert and Wahl (1967a)

Potential Energy of Ar

E

a

v-'1 g

3.8 0.0015

4.0 -0.0230

4.2 -0.0369

4.3 -0.0411

4.5 -0.0453

4.6 -0.0458

4.7 -0.0458

5.0 -0.0424

5.5 -0.0328 oO

0.0600

0.0228

0.0065

0.1188

0.0599

0.0298

0.1901

0.1154

0.0712

a. Hartree-Fock

Gilbert and Wahl (1967a)

113
Potential Energy of Cl„ , ^

-S

3.6

918.9823

3.8

918.9871

3.9

918.9858

4.2

918.9727

-E

3°g

40

g 50c

104.8909 104.8976

10.6172 10.6216

8.0861 8.0901

1.2506 1.2162

.6153 .5964

104.9006

10.6237

8.0921

1.2017

.5868

104.9082

10.6292

8.0972

1.1673

.5583

lo„

3ou

40..

104.8909

10.6170

8.0858

1.0067

104.8976

10.6215

8.0899

1.0197

104.9006

10.6236

8.0919

1.0256

104.9082

10.6291

8.0971

1.0407

in

u

2 n

8.0810

.5831

8.0856

.5680

8.0877

.5616

8.0932

.5463

3.6 3.8 3.9 .2

i n

g 2 nD

8.0810

.4358

8.0856

.4480

8.0877

.4534

8.0933

.4668

Gilbert and Wahl (1967c)

114
Potential Energy of Cl,

h

+ V

3.8

4.0

4.5

4.7

5.0a

5.1

5.5

6.0

7.0

8.0

9.0

b

0.0346

0.0017

-0.0387

-0.0444

-0.0472

-0.0471

-0.0435

-0.0361

-0.0721

-0.0131

-0.0075

0.1955

0.1402

0.0577

0.0213

0.0171

0.0008

-0.0010

-0.0008

-0.0001

b.

104.6033, 10.3252, 7.7930, 0.8380, 0.2542,

104.6033, 10.3252, 7.7930, 0.7904, 0.1915,

7.7913, 0.2492, 7.7913, 0.2124

(Clj) = -919.0204

0.3104 0.3674

0.2357 0.2915

0.1181 0.1646

0.0598

0.0523

0.0946

0.0849

0.0168 0.0335

0.0057 0.0126

0.0020 0.0042

0.0011 0.0011

c. Hartree-Fock

Gilbert and Wahl (1967a, b)

Potential Energy curves of He Ne +

-E

2^

0.5

1.0

1.5 129.6685

2.0 130.0612

3.0 130.2145

117.2660

127.2128

129.1541

129.8814

130.1984

2E+

*

128.9913

129.4127

129.7877

4.0 130.2274

5.0 130.2273

6.0

130.2245

130.2254

130.2247

129.8182

129.8128

Michels (1967)

115
Potential Energy of NaLi

Hartree-Fock Extended Hartree-Fock

4.0

5.0

5.5

6.0

169.26357

169.28917

169.29136

169.29073

169.28938

169.31231

169.31422

169.31236

Jei'tonclni and Wahl (1967)

Potential Energy of NaF

-E

3.1

3.5

4.0

4.5

6.0

12.0

Hartree-Fock

261.3495

261.3773

261.3722

261.3561

261.3030

Extended Hartree-Fock (OVC)

261.3710

261.3991

261.3951

261.3797

261.3262

261.2659

261.2662

Das and Wahl (1967)

116
Potential Energy Curves of BeH

-E

xl4'

1.5 2.0 15.6063

2.5 15.7202

3.0 15.7159

3.5 15.6696

-'t.O 15.6363

4.5 15.5485 oO 15.5481

14 7013

L5 1374

15.4626

15.5123

15.5701

15.5156

Michels (1967)

Potential and Orbital Energies of KCN

Lo 2-5a2 in 4

, ^

1.81287

1.81287

1 .9343

1.9343

2.00899

2.00399

2.0143

2.0843

2.0843

2.23221

1.96119

2.38053

2.1091

2.2491

1.76507

2.60325

2.179i

a

2.1091

2.2491

1.96119

92.8841 15.5560,11.2303,1.2906,0.3403,

0.5753, 0.5370

92.8680 15.6362,11.3200,1.1903,0.3718,

0.5898, 0.4696

92.9160 15.5850,11.2738,1.2543,0.8244,

0.5810, 0.5089

92.9052 15.6118,11.3010,1.2200,0.8352,

0.5853, 0.4867

92.7663 15. 5136, 11. 21 13,1. 3303, 0.7310,

0.5597, 0.5792

92.8065 15.6667,11.3641,1.1405,0.8467,

0.5835, 0.4416

92.9147 15.5973,11.2907,1.2365,0.812 9,

0.5820,0.4968

92.9153 15.5835,11.27 97,1.2534,0.7930,

0.5786, 0.5077

92 . 9048 15.6101,11. 3068 ,1.2187,0. 8043

,

0.5824, 0.4855

92.8826 15.5520,11.2558,1.2888,0.7522,

0.5700, 0.5340

117
2.23221

2.47026

2. 3805 I

2.14243

92.3684 15.6314,11.3357,1.1361,0.7376,

0.5300, 0.4660

.2.3846 15.5364,11.2933,1.2425,0.7277,

0.5717, 0.4992

a. Exp. R

McLean and Yoshimine (1967)

1.72311

1.91457

1.91457

2.10603

2.11633

2.1273

2.34003

2.35143

2.53663

Potential and Orbital Energies of N2 ia 2 - 7<J 2 Hi4 2E4

, 1£

f

2.20903

2.01762

2.45453

2.69998

1.31586

2.2418

2.46598

2.01762

2.21938

183.6268

133.7204

183.7342

183. 7169

133.6447

183.7567

133.6841

183.6953

183.6310

20.5974,15.7855,15.6358,1.7055,1.4948,

0.7831,0.6984,0.8458,0.5043

20.6334,15.8097,15.6255,1.7200,1.5086,

0.8305,0.6758,0.8370,0.4971

20.6163,15.8042,15.6931,1.6239,1.4010,

0.797 9,0.7103,0.7/04,0.5002

20.6303,15.8113,15.7395,1.5369,1.3300,

0.3215,0.7005,0.7048,0.5016

20.6335,15.8287,15.5998,1.8555,1.4151,

0.8867, 0.6452, 0,.8337, 0.4594

20.6505,15.8403,15.6947,1.6105,1.4240,

0.8315, 0.6987, 0.7613,0.4914

20.6610, 15.8580,15.7511,1.5139,1.3491,

0.3464, 0.6979, 0.6993, 0.4874

20.6993,15.8579,15.6633, 1.7357,1.3342,

0.8810, 0.6769, 0.3071, 0.4554

20."/ 108, 15. 3783, 15. 7217, 1.6263, 1.2667,

0.8824, 0.6912, 0.7399,0.4516

Exp.

McLean and Yoshimine (1967)

118
Energy As A Function of the Internuclear Distance

(H2 F)" (Iff 4o

1.74

1.85 1.95

1.80

2.20

2.20

2.40 2.70

2.70 3.00

3.10

3.60

Rhh

3.00

2.35

2.20

2.10

1.90 1.80

1.60

1.40

1.80 1.50

1.45

1.40

-100.517

-100.569 -100.574

-100.567 -100.574*

-100.575

-100.577 -100.582 -100.577*

-100.577*

-100.585 -100.586

-100.574

a. Potential energy along the reaction coordinate except for the points marked with an asterik

Ritchie and King (1966)

3.0 4.0 5.0 R(ATOMIC UNITS)

Fig. 1. Potential energy curves for ground and excited states of BH.

119
100 .1 I I

I

I

I I I I

I

I I I I

I

I I

I I

I

I I I I

I

I I I I.

-LCAO

OSCF

— 100

INTERNUCLEAR DISTANCE R (Bohrs)

2. He-He potential curves. LCAO - linear combination of atomic orbitals method.

OSCF - optimized self-consistent-field (Hartree-Fock) method. Other curves represent Thomas-Fermi -Dirac (TFD) or semi- empirical calculations. For references see original paper

by Gilbert and Wahl (1967).

3.0 INTERNUCLEAR

4.0 DISTANCE R (Bohrs) Fig. 3. Ne-Ne potential curves. LCAO - linear combination of atomic orbitals method. AASCF - augmented asymptotic self-consistent-field method. Other curves represent Thomas-Fermi -Dirac (TFD) or semi- empirical calculations. For references see original paper

by Gilbert and Wahl (1967).

120
1.000

0.100 -

V(au)

0.010

0.001

0.0001

Fig. 4. Potential curves of

HeNe, HeAr, NeAr. Computed

interatomic potential energy

V in Hartree atomic units

(e2 /a

Q

), relative to Hartree-Fock energy of sepa- rated atoms, plotted against nuclear separation R in Bohr

atomic units (a ) . Computed

points are indicated. The heavy lines are simple exponential functions fitted to these points, V = Ay exp

(-XVR). The parameters for HeNe, HeAr, NeAr are, res- pectively, Ay = 33.A18, 31.395, 92.544 and > v

= 2.322, 1.884, 1.923.

Fig. 5. Li„ potential curve. Com- parison of extended Hartree-Fock

theory with experiment.

14.85

i | I I

i

i | 1 1 1 1 | 1

\ LIMIT OF HARTREE-FOCK ATOMS

1

1 1

14.87

SEVEN //

CONFIGURATION If -

14.89 ~

1 J

-

\^-^-HULBERT-HIRSCHFELDER -

14.91 i 1 I I > i 1 i I I I 1 I I , 1 1 10R(BOHRS) 20

121
-48.97 -

-49.01

-49.05

cc -49.07 -

-49.09

-49.13 -

-49.15 I L

Fig. 6. Potential curves of the ten lowest elec- tronic states of Bo calculated using configura- tion interaction based on SCF molecular

orbitals.

2.0 3.0 3.5 R(BOHRS)

R(A°)

Fig. 7. Potential curves of the ten lowest electronic states of C2 calculated using configuration

interaction based on SCF molecular

orbitals. The energy zero for the computed curves is chosen such

that both computed and experimental

curves approach the same asymptotic

limits for all states which dissociate to a pair of normal ( P) atoms. Primed numbers refer to experimental

results

.

.0 1.5 2.C 2.5 3.0 3.5 4.0 .20 - w 1

1 1 1

" C('D)+C('S)

.15 -

- \\/~

10 C{'D) + C('D)

.10 -

—

l\§/(

\ \ /

1 1 \ \

'

C( 3 P) + C('D) .05 w\ -

I Vz-jk^" ~x

II — v£^</'

C( S P) + C( 3 P)

KEY

1 III *' \8 *• A/ /

II l\ \' // / /f n,n' STATE

.05 W\w/, // I x 'ij Wx-//// /

2 x"nu

-.10

lull I'll

1\1 \\ I

1 1 n

3 A'

3 s^ —

\ x^\^ 1 / //

4

5

b. 'nu A"'X U

\ Yv 4/// 6 A

5IIg -.15 \\ 3 4,1

7 C 'Ilg 8 b

5n, l\\2//

» \5#' 9 d 'IB .20 A3' ', \\ "2

10

1

e 'ij

1 1

12

10

9

8

v(ev) - 5

- 4

- 3

4 5 R(a )

122
i—i—I—i—i—i—I—i—

r

108.10

-108.15

-108.20

-108.25

-108.30

-108.35

-108.40

-108.45

/ B

2 lJ

*

"•.

-109.00

/x2 li / 9 .-"

Tf-m--x

D..„am

....X- A

2 D

Nj states

J L J I I I L

"i I i I I r

\_Q20 & ' 5,."'

V6 B

12

V'

,

)2v +

i 5 1* b4

« D 3 • 6 2 '•5 'a A

2 n

..XI- •'

'a v a-' ,' • 3'•2 Vi „ ...-

-108.75

-108.80

- 108.85

108.90

-108.95

109.00

-109.05

-109.10

E(hortree)

-109.15

-109.20

-109.25

-109.30

-109.35

-109.40

-109.45

-109.50

-109.55

-109.60 J I I I I I I I L

1.8 2.0 2.2 2.4 2.6 1.8 2.0 2.2 2.4 2.6 R(bohr)

(o) R(bohr)

(b)

Fig. 8. Potential curves, E(R), for N„(X h, +

) and N„+

(X h

+

, A

2

I1 , 2_ + E 2 g

' u' B % ): (a) calculated EU_(R) results; (b) E„, fR) results

u rir RKK

of Gilmore. Note ordinate scale the same but ranges are different.

123
-197.85

-197.90-

-198.70

-198.75

-198.80

-198.85

F + F(2£ -HT

F + F(HF)

2.5 3.0 3.5 INTERNUCLEAR SEPARATION, BOHRS4.0

is. 9. Potential curves for the ground

E state of F

2

. VCI - Valence config- uration interaction; STO - Slater-type

orbital; HFAO - Hartree-Fock atomic

orbital designate Valence Bond calculations of Harris and Michels (1967). They reference the SCF and ODC (ex- tended Hartree-Fock) calculations.

-198.7

<n

UJ

UJ

CEH

cc<

Ts— -198

>-

(.3

or. UJ

Fig. 10. Extended Hartree-Fock poten-

-198.9

1 1 1 COMPUTED POTENTIAL CURVES

FOR THE FLUORINE MOLECULE

HARTREE FOCK LIMIT 2 F ATOMS^co

*-y*-- OVC (3CTg ONLY DISTURBED)

0VC(3CTU FILLED FROM n = 2 LEVEL)

f EXPT

± I 2.0 3.0 4.0 5.0 6.0

INTERNUCLEAR DISTANCE (BOHRS)

124
-169.240

1

1 1 i i i L^^" 1

-

-169.260

Id

LU

<r\-<

I

/hartree fock -

g-169.280 _

tu

LU Na( 2

S) + Li( 2S)

-169.300 -

v/ovc -

-169.320 1

1

1 4.0 6.0 8.0 10.0 INTERNUCLEAR DISTANCE (BOHRS)

12.0

Fig. 11. Extended Hartree-Fock potential curves for LiNa.

261

261.2

UJ

orhCC<

Xo 261.3

or

261.4

HARTREE FOCK Na+F ASYMPTOTE

OVC Na+F ASYMPTOTE

OVC (IONIC)

Na F NEUTRAL(HF)ATOMS

A h

2.0 6.0 10.0 14.0 16.0 20.0

INTERNUCLEAR DISTANCE (BOHRS)

Fig. 12. Extended Hartree-Fock potential curves for NaF.

125
Fig. 13. Energy surface, linear H . Minimize energy variance.

CALCULATED SURFACE

2.5-

2.0-

Fig. 14. Energy surface, linear H . Configuration interaction based on pseudo-natural orbitals.

126
-79.1440

t_ -79.1460

-79.1480

n

1

1 T

0- Fig. 15. Barrier to internal rotation in ethane.

30 60 90 120 150 180 X (Degrees)

Fig. 16. Barrier to internal rotation in methyl alcohol.

-114.933

-114.936

"i i

1 1 p

14.934- I'

0.002

0.001 z

0.000 x

30 60 90 120 150 180 X (Degrees)

Fig. 17. Reaction surface for NH +

NH4

C1 (horizontal valley) or NH^ + CI NH4 C1 (vertical valley). The abscissa

gives the N-H(4) distances; the ordinate

gives the H(4)-C1 distances. Each en- ergy contour represents steps of 0.025

a.u. <= 0.68 e.V.)

.
L. Gaussian Basis Calculations ! Introduction

These results are included for the chemist; they illustrate the beginning

of a capability to handle fairly large systems. The future may see the use

of different basis sets or techniques and the economics of the calculations may radically alter but it is now possible to obtain H. F. approximations to large systems at more than a minimal level. They have been applied to the calculation of internal rotation barriers, the surface of a chemical reaction

and to the general understanding of the molecular shell structure and bonding

characteristics. The success or lack of it at this time can be gauged by

reference to the following studies. This area is moving rapidly and the conclusions obtained from these references may be very temporary but it is incontestable that large molecules can now be meaningfully treated by ab initio calculation.

a Basis 36 I 3TF's cont

Symmetry D

3d

Geometry C-C 2.915878

Total energy -79.1082

Orbital energies

la,2u 11.2141

la, 11.2142

2a lg 1.0427

2a

2g 0.8544

le

u 0.6191

33 lg 0.5094

le . 50.66

D3h

C-H 2.0325 79.1025

la 2

" 11.2127

la' 11.2126

2 2a| 1.0423

2aJ" 0.8537

le' 0.6139

3a' 0.5089

le" 0.5050

Clementi and Davis (1966)

a. Best atom basis, Huzinaga (1965)

128
Basis See a. Symmetry

*2H

6

2h

54 GTF (B 9s,3p)

b Geometry See fig. 1 Buenker et al (1966); B-B 1.70, BH, 2.55, BH

3 2.30, < BBH, 49' 8 0"

Total energy

Orbital energies

la

lb lu

2a.

2b

lb

lb

lu

3u

'2u

3ag

lb 3g

-52.7551

7.6484

7.6479

0.8734

J. 6427

0.5493

0.5285

0.5205

0.4744

Reference Buenker et al (1966)

a. Linear combination of GTF, Whitten (1966); decomposed

long-range p component; long-range S group.

b. B - dihedral angle between yz plane and H B H plane.

3 2 4

-52.753

7.6416

7.6410

0.8979

0.6457

0.5558

0.5546

0.5174

0.'737

Bunielle and Kaufman (1965)

Basis Linear combination of GTF; decomposed long-range

s and p components.

Symmetry D~ ,

Geometry C-C 2.^5102 , C-H 2.0236 , < HCH 117°

Total energy

Orbital energies

la.lg

lb 3u

2a lg 2b

3u

lb.'2u 3a

lb

lg

'lg

lb lu

Whitten (1966)

-78.0012

-6

11.2341

11.2326

1.0324

0.7937

0.6462

0.5847

0.5063

0.3676

129
C

3H6

Basis Best atom linear combinations of 60s, 45p lobe functions.

Symmetry D 3h

Geometry C-C 2.880, C-H 2.022, < CCC 60° , < HCH 120°

Total energy -116.9164

Orbital energies -e

la

l 11.2941

le' 11.2935

2*[ 1.1510

2e' 0.8344

la"

2 0.7024

3*1 0.6257

le" 0.5460

3e' 0.4398

Whitten (1966)

Buenker et al (1967b)

C

4H2

5est atom, Huzinaga (1965) C 9s,5 P ;H 3s.

Symmetry D

Geometry C-C 2.2772, C-C 2.6060, C-H 2.0107

Total energy -152.127 ± 0.004a

Orbital energies _ £ o o . n n

g u u g

11.536 11.532 0.592 0.472

11.481 11.481

1.163 1.106

0.936 0.790

0.776

a. Errors correspond to predetermined accuracy for integrals.

Snyder (1967)

130
Cflfi

; cis, trans butadiene

Basis Best atom linear combinations of 70s, 60p lobe functions.

Symmetry

2v trans C

2h

Geometry

H.-C,

«z

L --^ C-4" H5- K " 3

CIS

x, y, z

e

l -2.66438,0,0

c 2 -1.40116,2.18796,0

Hi -4.70518,0,0

trans

H

2 -1.64398,-1.76738,0

H, -2.42156,3.95534,0

Total energies -154.7023

c

l -3.2768, 1.183,0

c 2 -0.7502, 1.183,0

H

l -4.2916, 2.9537,0

H, -4.2916, -0.5877,0

H 3 0.264, 2.9537,0

-154 .7103

Orbital energies 1*1 11.3463

lb 2 11.3457

2b 2 11.3045

2a

1 11.3045

3* 1 1.1155

3b

2 1.0109 u 1 0.8570

4b

2 0.7442

5a

l 0.7073

6a . 0.6292

5b

2 0.6022

6b

2 0.5370

7a

l 0.5261

lb

l 0.4768

la„ 0.3541

U 8 11.3466

lbu 11.3459

2b „ 11.3098

2a

g 11.3098

3a

8 1.1089

3bu 1.0214

*a

8 0.8331

4bu 0.7751

5a

8 0.6638

5b

u 0.6603

6a

g 0.5742

6b u 0.5693

7a

8 0.5140

la

u 0.4765

lb„ 0.3579

a. Whitten (1966)

Whitten and Buenker (1967)

131
H

2CO

Basis Linear combination of GTF; decomposed long-range s and p components.

Symmetry C 2v Geometry C-0 2.2864, C-H 2.18, < HCH 120° Total energy -113.8094

Orbital energies -e

l3

l 20.579

2a

1 11.352

3a

l 1.422

4aj 0.864

lb 2 0.700

5a

l 0.635

lb

1 0.527

2b2 0.437

Dipole moment ( H„C 0") 3.4

Buenker and Whitten (1967)

Formamlde (CH3NO)

Basis: 87 GTF ' s grouped into 36 basis

functions (Best Atom Bouble Zeta)

Formic Acid (CH.O^

83 GTF's grouped into 34 basis

functions (Best Atom Double Zeta)

Symmetry: C (one reflection plane)

Geometry: C=0 2.3489 C-N 2.5379 C-H 2.0674 N-H 1.8803

Total Energies:-168.8661

Orbital Energies:

la' 2a' 3a' 4a'

1 5a

6a'

7a' 8a'

9a' 10a' la" 2a"

Dipole Moment

Comments:

Basch (1967)

-e

20.5325

15.5939

11.3867 1.3939

1.2388 0.8766

0.7669

0.6719

0.6012

0.4365

0.5774 0.4164

4.95 Debyes

C=0 2.2715 C-0(H)2.5379

C-H 2.0730

0-H 1.8368

-188.6877

20.6248 20.5819

11.4302

1.5114

1.4042 0.9084

0.7413

0.7137 0.6019

0.4809

0.6521 0.5000

1.49 Debyes

Also one non-planar geometry and several excited

triplet states (planar geometry) in same basis.

132
CH

3F

Basis 3

57 GTF's contracted to 28 basis functions.

Symmetry C,

Geometry C-H 2.088, C-F 2.617

< HCH 109°54°, < HCF 109°02 1

Total Energy -138.94979

Orbital Energies -e

la

l 26.23270

2a

l 11.31825

3a l 1.55533

4a 0.94912

5a

l 0.65554

le 0.69095

2e 0.52736

a. Best atom basis, Huzinaga (1965) Krauss (1967)

Ethyl Fluoride (C H F)

Basis: 104 GTF s grouped into 23 basis functions (Hartree-Fock AO Basis).

Symmetry: C (one reflection plane).

Geometry: C-C 2.9102, C-F 2.5984, C-H 2.0919 Staggered Eclipsed

Total Energy: -177.9409 -177.9368

Orbital Energies: -e -e

la' 26.141 26.140

2a' 11.396 11.395

3a' 11.266 11.264

4a' 1.548 1.548

5a' 1.032 1.032

6a' 0.860 0.860

7a' 0.668 0.669

8a' 0.624 0.622

9a' 0.548 0.545

10a' 0.486 0.486

la" 0.697 0.696

2a" 0.569 0.573

3a" 0.490 0.487 Dipole Moment: 2.56 Debyes 2.52 Debyes

Basch (1967) 133
CHS, Pyrrole

4 5

Symmetry C 2v

Geometry See b.

Total energy -207.9313

Orbital energies

a

± (P) b

2 (°)

15.7100 11.4253

11.4252 11.3785

11.3793 1.0345

1.3239 0.7970

1.0955 0.6243

0.8251 0.6022

0.7779

0.6476

0.5766

a. Best atom basis, Huzinaga (1965)

b. Equilibrium value Sutton (1958)

Clement! (1967b)

b^II) a

2

(Il)

0.6313 0.3879

U.4253

134
CHS, Eyridine

Basis a 111 GTF's contrac tec1 to 35 basis functt'yns

Symmetry C 2v

Geometry X y X y

N 0.0 1.328750 C

l -2.18521 0.0

H

l -3.94316 1.029325 C

2 2.18521 0.0

»2 3.94316 1.029325 C

3 -2.26896 -2.60938

H

3 4.06176 -3.58167 C 2.26896 -2.60938

H4 4.06176 -3.58167 c

5 0.0 -3.97052

Hc 0.0 -6,0075

5

Total energy -245.6219

Orbital energies

3l (0) b2

(Cf)

15.6775 11.4611

11.4611 11.4344

11.4430 1.1102

11.4343 0.9043

1.3277 0.7260

1.1577 0.6700

0.9218 0.5795

0.7791

0.7012

0.6394

0.4654

Mil) a2

(H)

0.6223 0.4472

0.4586

a. Best atom basis, Huzinaga (1965)

Cleaenti (1967c)

135
C H N , Pyrazine

4 4 2

Basis 108 GTF ' s contracted to 34 basis functions

Symmetry C 2v

Geometry C-N 2.5512 C-C 2.62674 C-H 2.0598

Total energy -261.5543

Orbital energies -e

a

i (0)

2 b

l (H)

15.6954 11.4765 0.6494

15.6953 11.4754 0.4935

11.4764 1.1326

11.4754 0.9310

1.3762 0.7552

1.2729 0.6837

0.9571 0.6107

0.7797

0.7228

0.5327

0.4412

a. Best atom basis, Huzinaga (1965)

Clementi (1967d)

*

2

(n>

0.4618

136
Li C H

Basis 72 GTF contracted to 51 basis functions

Symmetry C

Geometry C-C 2.69, C-H 2.02, Ring-Li 3.08

Total energy -196.2318

Ring-Li frequency is calculated as -> = 750 cm".

Janoschek et al (1967b)

C

6 H

6

Basis Best atom linear combinations of 90 s, 90p lobe functions

.

Symmetry D6h

Geometry C-C 2.64, C-H 2.048

Total energy -230.312

a. Whitten (1966)

Whitten et al (1967)

Basis 78 GTF contracted to 54 basis functions.

Symmetry D.,on

Geometry C-C 2.63 , C-H 2.04

Total energy -227.2695

Energies determined at sufficient points to determine tiie following frequencies

calc: Exp. u^ 1200 1000

"J 4110 3062

*

3 1376 1540

u> 1280

4

Janoscliek et al (1967a)

137
Acknowledg ement

The bulk of this report is abstracted either from very recentlypublished work or work that is still unpublished. Without acces'" to this information this project would have been unthinkable. It was

gratifying to find that many workers in this field were willing to take the considerable time required to summarize their unpublished

work. I believe it reflects a desire to take stock in a rapidly

moving field and to communicate a growing feeling of confidence

in the ability to calculate meaningful molecular energies and

properties,

Ths list of contributors is listed below in alphabetical order. I wish to thank them all for their effort and the speed of the response. The organization of their material is my responsibility

alone, and I apologize beforehand to all -who will find the organization

is not properly responsive to the material.

I have also included addresses of the individuals since they can

best answer inquiries as to their unpublished material.

For the considerable clerical and typing assistance I -wish to thank Miss Patricia Ann Foreman and Mrs. Judith F. Frye.

Allen, Leland

Department of Chemistry, Princeton University, Princeton,

New Jersey 08540. Barnett, G. P. Theoretical Physics Group, Lockheed Research Laboratory,

Palo Alto, California 94301.

Baschj Harold

Bell Telephone Laboratories, Murray Hill, New Jersey 07971

Cade, Paul E. Laboratory of Molecular Structure and Spectra, Department of Physics, University of Chicago, Chicago, Illinois 60637

Clementi, Enrico

IBM Research Laboratory, Monterey and Cottle Roads,

San Jose, California 95114

Conroy, H. Mellon Institute, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213

Csizmadia, I. G. Department of Chemistry, University of Toronto, Toronto, Canada

Davidson, Ernest R. Department of Chemistry, University of Washington, Seattle,

Washington 98105

Diercksen, Geerd Max Planck-Institut fur Physik und Astrophysik, 8000 Munchen 23, Fohringer Ring 6, Munich, Germany

Kaufman, Joyce J. RIAS, 1450 S. Rolling Road, Baltimore, Maryland 21227

King, H. F. Department of Chemistry, State University of New York at Buffalo,

Buffalo, New York 14214

Matcha, Robert L. Battelle Memorial Institute, 505 King Avenue, Columbus, Ohio 43201

Michels, H. H. United Aircraft Research Laboratories, United Aircraft Corporation, East Hartford, Connecticut 06108

138
McLean, A. D. San Jose Research Laboratory, IBM, Monterey and Cottle Roads, San Jose, California 95114

Nesbet, R. K. IBM Research Laboratory, San Jose, California 95114

Pederson, L. Department of Chemistry, Harvard University, Cambridge, Massachusetts 02138

Preuss, H. Max-Planck-Institut fur Physik und Astrophysik, Institut fur Astrophysik, Munich 23, Germany

Ransil, Bernard Boston City Hospital, Thorndike Memorial Laboratory,

818 Harrison Avenue, Boston, Massachusetts 02118

Richards, Graham

Physical Chemistry Laboratory, South Parks Road,

Oxford, England

Schwartz, Maurice E. Princeton University, Department of Chemistry, Princeton,

New Jersey 08540

Snyder, Lawrence C. Bell Telephone Laboratories, Murray Hill, New Jersey 07971

Stevens, Richard M. Department of Chemistry, Harvard University, 12 Oxford

Street, Cambridge, Massachusetts 02139

Wahl, Arnold C. Chemistry Division, Argonne National Laboratory, Argonne,

Illinois 60439

Whitten, Jerry

Department of Chemistry, State University of New York at Stony Brook, Stony Brook, New York 11790

Yoshimine, M.

San Jose Research Laboratory, IBM, Monterey and Cottle Roads,

San Jose, California 95114

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