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Tables of Molecular Vibrational

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Tables of

Molecular Vibrational Frequencies

Part 1.

UNITED STATES DEPARTMENT OF COMMERCE

Alexander B. Trowbridge, Acting Secretary,

NATIONAL BUREAU OF STANDARDS A. V. Astin, Director

Takehiko Shimanouchi

University of Tokyo

Tokyo, Japan

NSRDS-NBS 6

National Standard Reference Data SeriesNational Bureau of Standards 6

(Category 3— Atomic and Molecular Properties)

Issued March 1, 1967

For sale by the Superintendent of Documents, U.S. Government Printing Office Washington, D.C., 20402 - Price 40 cents
NATIONAL BUREAU OF STANDARDS

JUN 9 1970

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Cop. 'L

Library of Congress Catalog Card Number: 66—60085
Foreword

The National Standard Reference Data System is a government-wide effort to give to the

technical community of the United States optimum access to the quantitative data of physical

science, critically evaluated and compiled for convenience. This program was established in

1963 by the President’s Office of Science and Technology, acting upon the recommendation of the

Federal Council for Science and Technology. The National Bureau of Standards has been as- signed responsibility for administering the effort. The general objective of the System is to coordinate and integrate existing data evaluation and compilation activities into a systematic, comprehensive program, supplementing and expanding technical coverage when necessary, establishing and maintaining standards for the output of the participating groups, and providing mechanisms for the dissemination of the output as required.

The NSRDS is conducted as a decentralized operation of nation-wide scope with central co- ordination by NBS. It comprises a complex of data centers and other activities, carried on in

government agencies, academic institutions, and nongovernmental laboratories. The independent

operational status of existing critical data projects is maintained and encouraged. Data centers

that are components of the NSRDS produce compilations of critically evaluated data, critical re- views of the state of quantitative knowledge in specialized areas, and computations of useful

functions derived from standard reference data.

For operational purposes, NSRDS compilation activites are organized into seven categories

as listed below. The data publications of the NSRDS, which may consist of monographs, looseleaf sheets, computer tapes, or any other useful product, will be classified as belonging to one

or another of these categories. An additional “General” category of NSRDS publications will

include reports on detailed classification schemes, lists of compilations considered to be Standard

Reference Data, status reports, and similar material. Thus, NSRDS publications will appear in

the following eight categories:

Category

12

3

4

5

6

7

8

Title

General

Nuclear Properties

Atomic and Molecular Properties

Solid State Properties

Thermodynamic and Transport Properties

Chemical Kinetics

Colloid and Surface Properties

Mechanical Properties of Materials

The present compilation is in category 3 of the above list. It constitutes the sixth publication

in a new NBS series known as the National Standard Reference Data Series.

A. V. Astin, Director.

Ill
Contents

Foreword

I. Introduction

List of Tables

Page Page

III II. Explanation of tables 3

1 III. Tables of vibrational frequencies 5

1. Ammonia, NH3 7 2 . Ammonia-e?3 , ND3 7

3. Phosphine, PH3 8

4. Phosphine-c?3 , PD3 8

5. Arsine, AsHs 9

6. Arsine-^3 , AsD3 9

7. Stibine, SbH3 10

8. Stibine-<f3 , SbD3 10

9. Carbon tetrafluoride, CF4 11 10. Carbon tetrachloride, CCLj 11 11 . Carbon tetrabromide, CBr4 12

12. Carbon tetraiodide, CI4 12

13. Dichloromethane, CH2 CI2 13

14. Dichloromethane-eh, CHDCI2 14

15. Dichloromethane-ck, CD2 CI2 15

16. Methane, CFL 16

17. Methane-c?i, CH3 D 16

18. Methane-ck, CH-2 D2 17

19. Methane-o?3 , CHD3 17 20. Methane-c?4 , CD4 18

21. Methanol, CH3 OH (gas) 19

22. Methanol, CH3 OH (liquid) 20

23. Methanol-eh, CH3 OD (gas) 21

24. Methanol-<L, CH3 OD (liquid) 22

25. Methanol-o?3 , CD3 OH (gas) 23

26. Methanol-G?3 , CD3 OH (liquid) 23

27. Methanol-G?4 , CD3 OD (gas) 24

28. Tetrafluoroethylene, CF2 CF2 25

29. Tetrachloroethylene, CCI2 CCI2 26

30. Tetrabromoethylene, CBr2 CBr2 27

31. 1 , 1 -Difluoro 2 , 2 -dichloroethylene, CF2 CCI2 27

32. trans-Difluorodichloroethylene, CFC1CFC1 28

33. Hexafluoroethane, CF3 CF3 29

34. Hexachloroethane, CCI3CCI3 30

35. Hexabromoethane, CBr3 CBr3 31

36. Ethylene, CH2 CH2 32

37. 1, 2-Dichloroethane, CH2 C1CH2 C1 (trans form) 33

38. 1, 2-Dichloroethane, CH2 C1CH2 C1 (gauche form) 34

39. 1, 2-Dibromoethane, CH2 BrCH2 Br (trans form) 35

40. 1, 2-Dibromoethane, CH2 BrCH2 Br (gauche form) 36

41. 1, 2-Chlorobromoethane, CH2 ClCH2 Br (trans

form) 37

42. 1 , 2-Chlorobromoethane, CH2 ClCH2 Br (gauche

form) 38

43. Ethyl fluoride, CH3CILF 39

44. Ethyl chloride, CtLCtLCl 40

45. Ethyl bromide, CFLCFLBr 41

46. Ethane, CH3CH3 42

47. Ethane-c^, CD3CD3 43

48. Dimethylether, CH3OCH3 44

49. Dimethylether-o?3 , CH3OCD3 45

50. Malononitrile, NCCH2 CN 46

51. Malononitrile-c(2 , NCCD2 CN 47

52. Ethylcyanide, CH3 CILCN 48

53. Propane, CH3 CH2 CH3 49

54. n-Butane, CH3 CH2 CH2 CH3 (trans form) 50

55. n-Butane, ChLCILCHiCHs (gauche form) 51

56. Benzene, CelL 52

57. Benzene-cL, CeDe 53

58. Cyclohexane, CeHi2 54

59. Cyclohexane-^12 , CeDi 2 56

IV
Tables of Molecular Vibrational Frequencies

Part 1.

T. Shimanouchi

A compilation of vibrational frequency data for selected molecules is being conducted

at the University of Tokyo in cooperation with the National Standard Reference Data Pro- gram of the National Bureau of Standards as a part of an international effort to compile and

evaluate physical and chemical data. This report, first of a series of annual reports, contains fundamental vibrational frequencies of 59 molecules together with vibrational assignments, sources of data, brief comments, and citations of references. The fundamental

frequencies are obtained mainly from the infrared and Raman spectra. When these are

not available, other experimental data such as microwave results are taken into account. The selection of vibrational fundamentals from observed spectral data is based upon

careful studies of the spectral data and comprehensive mathematical analyses. These

tables were designed to provide a concise summary needed for the computation of ideal gas thermodynamic properties. They may also provide a convenient source of information

to those who require vibrational energy levels and related properties in molecular spec- troscopy, analytical chemistry, and other fields of physics and chemistry.

Key Words: Molecular, vibrational, frequencies, data, tables, force, constants, spectral.

I. Introduction

A compilation of vibrational frequency data for selected

molecules is being conducted as a part of a broad program

on the compilation and critical evaluation of physical and

chemical data of many substances. Vibrational frequency

data of molecules are not only useful in research on molecular structure, but are also essential to accurate computation of ideal gas thermodynamic properties. These tables

will be a convenient source of information in any field of

physics or chemistry in which the vibrational energy levels and related properties are needed. These data may also be useful to those who utilize infrared or Raman spectra

as a technique in analytical chemistry.

This is the first of a series of annual reports being prepared

in cooperation with the National Standard Reference Data

Program of the National Bureau of Standards. It contains

fundamental vibrational frequencies and assignments for 59 molecules, as well as sources of data, brief comments,

and citations of references. The fundamental frequencies

are obtained mainly from the infrared and Raman spectra.

When this information is not available, other experimental

data such as microwave results are taken into account.

In many cases there are several possible ways of assigning

the observed frequencies of a molecule, and only tentative

assignments have been given in the literature. In the

present table the fundamental frequencies and assignments

are adopted only when they are definitely supported by the

calculation of normal vibrations based on a consistent set of force constants which correlate the frequencies of molecules having similar structures. These calculations also give reliable predictions for the frequencies of the optically

inactive vibrations.

The approach adopted in selecting force constants and

the techniques employed in calculating normal vibrations

are described in some detail in other publications by this author. The reader is directed especially to references

1 to 5. Further development of this expository material is contained in several papers now being prepared for publication. A later report in this series of Tables of Molecular

Vibration Frequencies will supply additional references.

Specific details may be found in several of the references

which follow the individual tables. General comments concerning the format and convention

adopted in this compilation are discussed below. The

objective was to achieve a very concise presentation of the

essential information in a form that would be useful in the

computation of thermodynamic properties. The molecules

included in this first report were selected from a list of

molecules that have been analyzed by mathematical tech- niques. It is hoped that this compilation can be continued

until all of the more important organic and inorganic molecules are included. Needless to say, there will be revisions

of these tables from time to time as new information becomes

available. The author of this report would appreciate

such information as well as comments concerning the scope

and format of the reports.

I express my sincere thanks to many members of the

National Bureau of Standards, especially C. W. Beckett,

D. R. Lide, Jr., and E. L. Brady who offered helpful suggestions in the planning of the tables.

I also acknowledge the assistance of my colleagues at the University of Tokyo: I. Nakagawa, C. Tanaka, S. Suzuki,

M. Tasumi, T. Fujiyama, J. Hiraishi, I. Harada, Y. Abo,

M. Oka, T. Ueda, M. Ishii, Y. Noto, and H. Yoshioka.

1
References

, [1] T. Shimanouchi, Pure and Applied Chemistry 7, 131 (1963).

[2] T. Shimanouchi, I. Nakagawa, J. Hiraishi and M. Ishii, J. Molecular Spectroscopy, in press.

[3] T. Shimanouchi and I. Suzuki, J. Chem. Phys. 42, 296 (1965), 43, 1854 (1965).

[4] H. Takahashi, T. Shimanouchi, K. Fukushima and T. Miya- zawa, J. Mol. Spectr. 13 , 43 (1964).

[5] M. Tasumi, T. Shimanouchi and T. Miyazawa, J. Mol. Spectr.

9, 261 (1962), 11 , 422 (1963).

2
II. Explanation of Tables

1. Observed fundamental vibrational frequencies in the

gaseous state are tabulated unless otherwise noted.

2. When vibrational frequencies in the liquid or the solid state are significantly different from those in the gaseous

state, they are tabulated on a separate sheet. (Examples:

CH3OH and CH3 CONHCH3 .) 3. The notation of Herzberg1 for the symmetry classes

and vibrational numbering is adopted unless otherwise

mentioned. In the case of deuterium compounds the same numbering used for the analogous hydrogen compound

is adopted.

4. “Approximate type of mode” is a descriptive name in- dicating the local symmetry coordinate which makes the

maximum contribution in the corresponding normal co- ordinates. (See below for the definition of the local symmetry coordinates of CH3 , CH2 , and CH groups.) When

there is a strong coupling among two or more symmetry

coordinates (more than 30% in the potential energy distri- bution), the notation (*>,-) is used, (vi) means that the contribution of the coordinate given in the vt row is also

considerable. The following abbreviations are used:

stretch. stretching twist. twisting

deform. deformation wag. wagging

rock. rocking bend. bending

sym.

anti. symmetric

antisymmetric

deg. degenerate

5. Observed infrared and Raman frequencies are tab- ulated, when available, for each normal mode. In addition

a selected value for the fundamental vibrational frequency

is listed. No corrections have been made for anharmonicity. As the selected value of frequency, that in the

gaseous state is adopted when available. When this is not

available, the value found in the liquid state, in the solid

state, or in solution is adopted. When no observed fre- quency is available, the calculated frequency is adopted.

Comments on the calculated frequencies are given in notes.

6. The uncertainties of the selected values are given

by the symbol. A, B, C, D, or E. The range of uncertainty

in cm"1 and the basis on which it is estimated is given in table I. Table I. Uncertainty uj the selected indue

Noia- 11 iicer- Basis*

tion tainty

cm ' A 0 ~ 1 (i) (las, grating spectrometer, rotational fine structure accurately

analyzed.

(ii) Gas, grating spectrometer, a sharp Q branch. B 1 ~ 3 (i) Gas, grating spectrometer, rotational fine structure partly

analyzed.

(ii) Gas, prism spectrometer, fairly high resolution (e.g., 700 — 1000 cm -1 for NaCI prism).

C 3 — 6 (i) Gas, prism spectrometer, low resolution (e.g., 1000 — 2000 cm 1 for NaCI prism).

(ii) Solid, liquid or solution, accurate measurement. D 6 - 15 (i) Gas prism spectrometer, very low resolution (e.g., > 2000

cm" 1 for NaCI prism).

(ii) Solid, 1 it] u id or solution, inaccurate measurement.

E 15 - 30 (i)

(ii) Value estimated from Fermi resonance doublet. Value estimated from overtone or combination tone.

(iii) Calculated frequency.

*The uncertainty assigned here to each method of measurement is a typical value; greater accuracy is often achieved with some of t he methods.

The intensity of a Raman line may also be indicated by

(1) ~ (10), which gives a rough estimation of relative in- tensity.

8. Abbreviations used in “comments” are as follows: FR Fermi Resonance with an overtone or a combination tone indicated in the parentheses

which follow OC Frequency estimated from an overtone or a combination tone indicated in the paren- theses

CF Calculated frequency

7.

Abbreviations used with “Infrared” and “Raman”

data are as follows:

ia inactive b broad

VS very strong vb very broad s strong sh shoulder

M medium P polarized

W

VW

weak

very weak

dp depolarized

1 G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand, New York,

1945).

3
SF Calculation shows that the frequency ap- proximately equals that of the vibration

indicated in the parentheses

TA Tentative assignment

OV Overlapped by the band indicated in the

parentheses

p

Depolarization degree.

9. “References” are not comprehensive. Only the papers

from which the data are taken or which contain important

information related to the given assignments are cited. The abbreviations, IR, R, and Th, denote infrared, Raman,

and theoretical, respectively.

10. The vibrational contributions to the ideal gas thermodynamic properties can be calculated from the fundamental

vibrational frequencies given in the tables. The statistical weight is one for the vibrations belonging to the species

designated by “a” and “6”, two for those designated by

“e” and three for those designated by The harmonic

vibration approximation can be used for almost all the vibra- tions except the torsional motions, the inversions of

NH3 -like molecules, and the ring puckering motions. For

these motions more refined treatments are needed especially

when the frequencies are low.

11. Definition of local symmetry coordinates:

(a) Local symmetry coordinates for the CH3 group (see

fig. la)

CH3 symmetrical stretching: (An + An + Ar3 )/V3

CH3 degenerate stretching: (2An — A

r

2 — Ar3 )/V6

CH3 symmetrical deformation: (Ar2 — Ar3 )/"\/2

(Aa23 + Aa3 i + A<*i 2 — A/3i — A/32 — A/33 )/V6

CH3 degenerate deformation: (2Aa23 — Aa3J — Aai2 )/ V6

(Aa3 i — Aai2 )/V2

CH3 rocking: (2A/3i — A/32 — A/33 )/\/6

(A/32 - Aj83)/V2.

(b) Local symmetry coordinates for the CH-2 group (see

fig. lb)

CH2 symmetrical stretching: (An + Ar2 )/V2

CH2 antisymmetrical stretching: (An — Ar2 )/V2

CH2 scissors: (4Aa — A/3 lx — A/32x — A/3 i Y — A/32 y )/\/2()

Crt2 wagging: (A/3i X + A/32x — A/3 i Y — A/32Y )/2 CH2 twisting: (A/3 i x — A/32x — A/3 i Y + A/32Y )/2 CH2 rocking: (A/3 i X — A/32x + A/3 Y — Ay82Y)/2.

(c) Local symmetry coordinates for the CH group (see

fig. lc)

CH stretching: ArCH CH bending: (2A^HX — A/3HY — A^HZ)/V

/6

(A/3hy — A/3 hz )/V2

(d) Local symmetry coordinates for the planar CH2 group (see fig. Id)

CH2 symmetrical stretching: (An + Ar2 )/V2

CH2 antisymmetrical stretching: (An — Ar2 )/V2^

CH2 scissors: (2Aa — A/3i — A/32 )/V6

CH2 rocking: (A)8i — A/32 )/\/2

CH2 wagging: A9X sin a.

(e) Local symmetry coordinates for the planar CH group

(see fig. le)

CH stretching: ArCH

in-plane CH bending: (A/3Hx — A/3Hy)/V2"

out-of-plane CH bending: A0H

' sin yXY .

H

FIGURE 1. Parameters of methyl, methylene, and methin groups.

4
III. Tables of Vibrational Frequencies

Pages 7 to 54

217-094 0-67-2

No. 1 Molecule: Ammonia NH3

Symmetry C:iv Symmetry number = 3

Selected

Sym.

class No.

Approximate

type of mode

value of

fre- quency

Infrared 3 Raman Comments

cm~ l cm~ l

V\ NH3 sym. stretch. 3337 A

(3336.2 s [3337.2 a

v-l NH3 sym. deform. 950 C [ 932.5 s

1 968.3 a

e NH3 deg. stretch. 3444 A

(3443.6 s (3443.9 a

V4 NH3 deg. deform. 1627 A

( 1626.1 s [1627.4 a

a “a” refers to the antisymmetric levels and “s” to the symmetric levels. (See

reference 2.) References

[ 1 ] IR.R. G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand,

New York, 1945) and references cited there.

[2] IR. W. S. Benedict and E. K. Plyer, Can. J. Phys. 35, 1235 (1957).

[3] IR. J. S. Garing, H. H. Nielsen, and K. N. Rao, J. Mol. Spectr. 3,496(1959).

[4] Th. J. L. Duncan and I. M. Mills, Spectrochim. Acta 20, 523 (1964). No. 2

Molecule: Ammonia-cfo ND3

Symmetry C3v Symmetry number= 3

Selected

Sym.

class

No.

Approximate

type of mode

value of

fre- quency

Infrared 3 Raman Comments

cm -1 cm~'

Oi V\ ND3 sym. stretch. 2420 A

(2420.1 s [2420.6 a

p2 ND3 sym. deform. 748 B

1 745.7 s

[ 749.4 a

€ Vi ND3 deg. stretch. 2564 A 2464.0

V4 ND3 deg. deform. 1191 B 1191

a “a” refers to the antisymmetric levels and “s” to the symmetric levels. References

[1] IR.R. G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand,

New York, 1945).

|2] IR. W. S. Benedict and E. K. Plyler, Can. J. Phys. 35, 1235 (1957).

13] Th. J. L. Duncan and I. M. Mills, Spectrochim. Acta 20, 523 (1964).

7
Molecule: Phosphine PH3

No. 3

Symmetry C3V Symmetry number =3

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ l cm~ x

a\ V\ PH3 sym. stretch. 2323 A 2322.9 2306

V2 PH3 sym. deform. 992 B 992.1 979

e V3 PH:J deg. stretch. 2328 B 2327.7

V4 PH3 deg. deform. 1118 A 1118.3 1115

References

[1] IR. R. Robertson and J. J. Fox, Proc. Roy. Soc. (London) A 120, 161 (1928).

[2] IR. L. W. Fung and E. F. Barker, Phys. Rev. 45 , 238 (1934).

[3] R. M. Yost and T. F. Anderson, J. Chem. Phys. 2, 624 (1934).

[4] IR. H. H. Nielsen, J. Chem. Phys. 20, 759 (1952).

[5] IR. V. M. McConaghie and H. H. Nielsen, J. Chem. Phys. 21, 1836 (1953).

[6] IR. J. M. Hoffman, H. H. Nielsen, and K. N. Rao, Z. Elektrochem. 64, 606 (1960).

[7] Th. J. L. Duncan and I. M. Mills, Spectrochim. Acta 20, 523 (1964).

Molecule: Phosphine-efa PD3

No. 4

Symmetry C3v Symmetry number =3

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman

cm 1 cm~'

«i V\ PD| sym. stretch. 1694 B 1694

v-> PD3 sym. deform. 730 B 730

e t'.t PD3 deg. stretch. 1700 D

V4 PD3 deg. deform. 806 B 806

References

[1] IR. E. Lee and C. K. Wu, Trans. Faraday Soc. 35, 1366 (1939).

[2] Th. J. L. Duncan and I. M. Mills, Spectrochim. Acta 20, 523 (1964).

8
Molecule: Arsine AsH3

No. 5

Symmetry C.i

v Symmetry number = 3

Sym.

class No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared 9 Raman Comments

cm

~ 1 cm~ 1

Ol V\ AsH;t sym. stretch. 2116 A 2116.1

V2 AsH3 sym. deform. 906 B

( 904.4 s

1 906.9 a

e V* AsH3 deg. stretch. 2123 B 2123.0

V* AsH.i deg. deform. 1003 B 1003

a “a” refers to the antisymmetric level and “s” to the symmetric level. (See

references 4 and 5.)

References

[1] IR. R. Robertson and J. J. Fox, Proc. Roy. Soc. (London) A 120, 161 (1928).

[2] IR. E. Lee and C. K. Wu, Trans. Faraday Soc. 35, 1366 (1939).

[3] IR. V. M. McConaghie and H. H. Nielsen, Phys. Rev. 75, 633 (1949).

[4] IR. H. H. Nielsen, J. Chem. Phys. 20, 759 (1952).

[5] IR. H. H. Nielsen, J. Chem. Phys. 20, 1955 (1952).

[6] Th. J. L. Duncan and I. M. Mills, Spectrochim. Acta 20, 523 (1964).

No. 6

Molecule: Arsine-efo AsD3

Symmetry C3v Symmetry number =3

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm -1 cm~ l

«i Vi AsD.-t sym. stretch. 1523 A 1523.1

V-2 AsD:t sym. deform. 660 B 660.0

e V* AsD3 deg. stretch. 1529 B 1529.3

Va AsD3 deg. deform. 714 B 714

References

[1] IR. E. Lee and C. K. Wu, Trans. Faraday Soc. 35, 1366 (1939).

[2] IR. V. M. McConaghie and H. H. Nielsen, Phys. Rev. 75, 633 (1949).

[3] Th. J. L. Duncan and I. M. Mills, Spectrochim. Acta 20, 523 (1964).

9
Molecule: Stibine SbH3

No. 7

Symmetry C,3

y Symmetry number= 3

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm

~ 1 cm~ x a x V\ SbH3 sym. stretch. 1891 A 1890.9

v-i SbH3 sym. deform. 782 B 781.5

e r3 SbH3 deg. stretch. 1894 B 1894.2

Va SbH3 deg. deform. 831 B 830.9

References

fl] IR. H. H. Nielsen, J. Chem. Phys. 20, 759 (1952).

[2] IR. W. H. Haynie and H. H. Nielsen, J. Chem. Phys. 21, 1839 (1953).

[3] Th. J. L. Duncan and I. M. Mills, Spectrochim. Acta 20, 523 (1964).

No. 8

Molecule: Stibine-efo SbD3

Symmetry C3V Symmetry number = 3

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~' cm ~

a\ V\ SbD3 sym. stretch. 1359 A 1358.8

v-1 SbD3 sym. deform. 561 B 561.1

e V:\ SbD3 deg. stretch. 1362 B 1362.0

Va SbD3 deg. deform. 593 B 592.5

References

[1] IR. W. H. Haynie and H. H. Nielsen, J. Chem. Phys. 21, 1839 (1953).

[2] Th. J. L. Duncan and I. M. Mills, Spectrochim. Acta 20, 523 (1964).

10
Molecule: Carbon tetrafluoride CF4 No. 9

Symmetry Td Symmetry number= 12

Sym.

class No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared

cm~'

Raman

cm -1 Comments

0.1 ", CF4 sym. stretch. 908 B ia 908.5 S

e v-i CF4 deg. deform. 435 B ia 435.0 S

h CF4 deg. stretch. 1283 D 1283 VS 1283.0 W FR(2r, 4 ). r4 CF4 deg. deform. 632 B 631.73 VS 631.2 S

References

[1] R.

[2] IR.

[3] IR. Th.

[4] IR.

[5] IR. Th.

[6] R.

[7] IR.

D. M. Yost, E. N. Lassettre, and S. T. Gross, J. Chem. Phys. 4, 325 (1936). C. R. Baeley, J. B. Hale, and J. W. Thompson, Proc. Roy. Soc. (London) 167, 555

(1938). E. K. Plyler and W. S. Benedict, J. Res. NBS 47, 202 (1951) RP2245.

P. J. H. Woltz and A. H. Nielsen, J. Chem. Phys. 20, 307 (1952). W. F. Edgell and R. E. Moynihan, J. Chem. Phys. 27, 155 (1957). B. Monostri and A. Weber, J. Chem. Phys. 33, 1867 (1960). A. Maki, E. K. Plyler, and R. Thibault, J. Chem. Phys. 37, 1899 (1962).

No. 10

Molecule: Carbon tetrachloride CCI4 Symmetry Td Symmetry number= 12

Selected

Sym.

class No.

Approximate

type of mode

value of

fre- quency

Infrared Raman Comments

cm~ i cm

~ 1 at V\ CCR sym. stretch. 458 C ia 458.7 (10)p

(liquid) e v2 CC14 deg. deform. 218 C ia 217.0 (7)dp

(liquid)

h V3 CCU deg. stretch. 776 E

1789 VS

[768 VS

1790.4 (4)dp

[761.7 (4)dp

FRti'i + j/4 ).

(liquid) r4 CCh deg. deform. 314 C 309.9 W 313.5 (9)dp

(liquid) (liquid)

References

[1] IR.R. G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand,

New York, 1945).

[2] R. J. P. Zietlow, F. F. Cleveland, and A. C. Meister, J. Chem. Phys. 18, 1076 (1950).

|3] IR. J. R. Madigan and F. F. Cleveland, J. Chem. Phys. 19, 119 (1951).

|4] IR. E. K. Plyler and W. S. Benedict, J. Res. NBS 47 , 202 (1951) RP2245.

[5] IR. H. Yoshinaga, J. Chem. Phys. 23, 2206 (1955).

(6j R. D. A. Long, D. C. Milner, and A. G. Thomas, Proc. Roy. Soc. (London) A2 40, 499

(1957).

[7] R. M. Ito, Spectroehim. Acta 21, 731 (1965).

11
No. 11

Molecule: Carbon tetrabromide CBr4

Symmetry Td Symmetry number = 12

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

«i V\ CBr4 sym. stretch. 267 C

cm~ l

ia

cm~'

(Benzene

soln.)

267 (7)p e v> CBr4 deg. deform. 123 C ia 122 (10)dp

ft V* CBr4 deg. stretch. 672 C 672 VS 671 (l)dp

Va CBr4 deg. deform. 183 C 182 (4)dp

References

[1] IR.R. G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand,

New York, 1945).

[2] R. A. G. Meister, S. E. Rosser, and F. F. Cleveland, J. Chem. Phys. 18, 346 (1950).

[3] IR.R. E. K. Plyler, W. H. Smith, and N. Acquista, J. Res. NBS 44, 503 (1950) RP2097.

[4] R. D. A. Long, D. C. Milner, and A. G. Thomas, Proc. Roy. Soc. (London) A240, 499

(1957).

No. 12

Molecule: Carbon tetraiodide CI4 Symmetry Td Symmetry number - 12

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

di V\ CI4 sym. stretch. 178 D

cm~'

ia cm -1 178(10)

e V-i CI4 deg. deform. 90 D ia

(solid)

90 (4)

ft Gi CI4 deg. stretch.

CI4 deg. deform.

555 D

123 E

555 VS

(solid)

r a 123 w

1127 W

(solid)

(solid)

123 (5) (solid)

a Crystal field splitting.

Reference

[1] IR.R. H. Stammreich, Y. Tovares, and D. Bassi, Spectrochim. Acta 17,661 (1961).

12
Molecule: Dichloromethane CH2CI2

No. 13

Symmetry C2V Symmetry number = 2

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm -1 cm -

a. V\ CH2 sym. stretch. 2999 B 2999 M 2996 S,p

1'2 CH2 scissors 1467 C 1467 W 1430.1 W,p

I'-.i CC12 sym. stretch. 717 B 717 M 713 S,p

V\ CC12 scissors 282 B 284 281.5 M,p

(liquid)

a-i C.-, CH2 twist. 1153 B iaa 1153 VW

b\ Vfi CH2 anti, stretch. 3040 B 3045 3040 S,dp

(liquid) v7 CH2 rock. 898 B 897.7 M 893 VW

bi Vh CH2 wag. 1268 A 1268 S 1265

(liquid)

v» CC12 anti, stretch. 758 B 758 VS

a In the spectrum of the liquid CH2 CI2 , a weak band is found at 1156 cm \ which

may be assigned to this vibration.

References

[1] IR. T. Shimanouchi and I. Suzuki, J. Mol. Spectry. 8, 222 (1962).

[2] IR.R. F. E. Palma, E. A. Piotrowski, S. Sundram, and F. F. Cleveland, J. Mol. Spectry. 13,

119(1964).

[3] R. H. L. Welsh, M. F. Crawford, T. R. Thomas, and C. R. Love, Can. J. Phys. 30,577

(1952).

13

217-094 0-67 -3
No. 14

Molecule: Dichloromethane-di CHDCI2 Symmetry Cs Symmetry number = 1

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ l cm

~ 1 (Liquid)

r a P\ CH stretch. 3024 B 3024 3019 M,p

v2 CD stretch. 2249 B 2249 2246 M,p

v3 CH bend. 1282 B 1282 1276 VW

f

787

P4 CD bend. 778 C

) (R-branch)

) 778

779 W,p

\ (liquid)

CC12 sym. stretch. 692 B 692 682 S,p

V6 CCI2 scissors 283 B 283 M,p

a" v2 CH bend. 1223 A 1222.9 1221 VW

Ph CD bend. 890 A 889.8 886 VW

Pit CCI2 anti, stretch. 738 B 738 725 W,dp

a Due to the strong p» band, the P-branch of this band is blurred out.

References

f 1 ] IR. T. Shimanouchi and I. Suzuki, J. Mol. Spectry, 8, 222 (1962).

[2] IR.R. F. E. Palma, E. A. Piotrowski, S. Sundram and F. F. Cleveland, J. Mol. Spectry. 13,

119 (1964).

14
Molecule: Dichloromethane-<i2 CD2 C12

No. 15

Symmetry C2v Symmetry number = 2

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm

~ 1 cm 1 (Liquid)

a, V\ CD2 sym. stretch. 2205 B 2205 W 2198 M,p

Vt CD2 scissors 1006 D

a 1006 W a 1052 VW,p

V-.\ CC12 sym. stretch. 687 B 687 M 677 VS,p

Va CC12 scissors 282 C 282 S,p

at V CD2 twist. 826 C ia 826 VW

6, c,i CD2 anti, stretch. 2304 C 2304 2304 VW

(liquid)

Vi CD2 rock. 712 D Calculated

from product rule.

b-t Vh CD2 wag. 957 B 957 VS

CC12 anti, stretch. 727 B 727 VS 716 W

a Palma et al., assigned a Raman line at 1052 cm 1 to this vibrational mode, although

the corresponding band does not appear in the infrared spectrum of CD2 C12 in the

gaseous and the liquid states. References

[1] IR. T. Shimanouchi and I. Suzuki, J. Mol. Spectry. 8, 222 (1962).

[2] IR.R. F. E. Palma, E. A. Piotrowski, S. Sundram, and F. F. Cleveland, J. Mol. Spectry. 13 , 118 (1964).

15
Molecule: Methane CHU

No. 16

Symmetry Td Symmetry number =12

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ l cm

~ 1

a\ V\ CH4 sym. stretch. 2917 A ia 2917.0

e v-l CH4 deg. deform. 1534 A ia 1533.6

ft V:\ CH4 deg. stretch. 3019 A 3018.9 3018.9

Va CH4 deg. deform. 1306 C 1306.2

References

[1] IR.R. G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand,

New York, 1945).

[2] IR. H. C. Allen, Jr. and E. K. Plyler, J. Chem. Phys. 26, 972 (1957).

[3] R. M. A. Thomas and H. L. Welsh, Can. J. Phys. 38, 1291 (1960).

Molecule: Methane-di CH3 D

No. 17

Symmetry C3v Symmetry number = 3

Selected

Sym.

class

No.

Approximate

type of mode

value of

fre- quency

Infrared Raman Comments

cm

~ 1 cm~ 1

Ol V\ CH.i sym. stretch. 2945 E

12973 M

[2914 M

FR(2iz-,).

v> CD stretch. 2200 A 2200.0 M

V* CH.i sym. deform. 1300 C 1300 M 1306

e V4 CH.i deg. stretch. 3017 B 3016.9 S

v* CH;i deg. deform. 1471 C 1471 W

v« C

H

3 rock. 1155 C 1155 M 1156

References

[1] IR.R. 6. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand,

New York, 1945).

[2] IR. J. K. Wilmshurst and H. J. Bernstein, Can. J. Chem. 35, 226 (1957).

[3] IR. H. C. Allen, Jr., and E. ICPlyler, J. Res. NBS 63, 145 (1959).

[4] IR. L. H. Jones, J. Mol. Spec. 4, 86 (1960).

16
Molecule: Methane-</2

No. 18

ch2 d2 Symmetry C2v Symmetry number= 2

Sym.

class No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm -cm

~ 1

a t V\ CH2 sym. stretch. 2976 D

f 2984 M

[2969 M

2974

J 2208 W

CD2 sym. stretch. 2202 C

| 2196 W

f 1442 W V3 CH2 scissors 1436 C

1 1430 W

Vi CD2 scissors 1033 C 1033 S 1034 a2 Va CH2 twist. 1329 C 1329 W

bt v6 CH2 anti, stretch. 3013 C 3013 S

Vi CH2 rock. 1090 C 1090 S 1090

b2 Vs CD2 anti, stretch. 2234 C 2234 M

v9 CH2 wag. 1234 C 1234 M

References

[1] IR.R. G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand,

New York, 1945).

[2] IR. J. K. Wilmshurst and H. J. Bernstein, Can. J. Chem. 35 , 226 (1957).

Molecule: Methane-d3 CHD3

No. 19

Symmetry C.3 V Symmetry number = 3

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Com ments

cm' 1 cm

~ 1

a, V\ CH stretch. 2993 C 2993 M

V-2 CD.t sym. stretch. 2142 C 2142 M 2141

Vs CD.) sym. deform. 1003 C 1003 M

e Vi CD:i deg. stretch. 2263 C 2263 M 2269

Vs CH bend. 1291 C 1291 M 1299

Vs CD.) deg. deform. 1036 C 1036 S 1046

References

[1] IR.R. G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand,

New York, 1945).

[2] IR. J. K. Wilmshurst and H. J. Bernstein, Can. J. Chem. 35 , 226 (1957).

17
Molecule: Methane-^

No. 20

CD4 Symmetry Td Symmetry number = 12

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

a\ Vl CD.| sym. stretch. 2109 B cm~ x

ia cm~ l 2108.9

e v2 CD4 deg. deform. 1092 B a 1092 1091.9

ft v3 CD4 deg. stretch. 2259 A 2259.3 2259.3

CD4 deg. deform. 996 B 996.0

a Coriolis interaction between v2 and v4 .

References

[1] IR.R. G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand.

New York, 1945).

[2] IR. H. M. Kaylor and A. H. Nielsen, J. Chem. Phys. 23, 2139 (1955).

[3] R. G. C. Shepherd and H. L. Welsh, J. Mol. Spectry. 1, 277

(1957).

[4] R. R. A. Olafson, M. A. Thomas, and H. L. Welsh, Can. J. Phys.

39, 419 (1961). *

18
Molecule: Methanol CH3OH (gas)

No. 21

Symmetry Cs Symmetry number = 1

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ x cm

~ 1

t a V\ OH stretch. 3681 A 3681 M

V2 CH,i deg. stretch. a 3005 C 3000 M

CH3 sym. stretch. 2844 A 2844 S

Va CH3 deg. deform. 1477 B 1477 M OV(C|„).

CH3 sym. deform. 1455 A 1455 M

n OH bend. (vt) 1345 B 1345 S

Vl CH3 rock. (cH ) b 1060 D 1060 W

Vh CO stretch. 1033 A 1033 VS 1032 (2)

it a V» CH3 deg. stretch. a 2965 C 2960 S 2955 (4)

I'll) CH3 deg. deform. 1477 B 1477 M ovum.

V\\ CH.t rock. ‘1165 C

Vvi C-O torsion d 270 D 50 ~ 860

a The value obtained by the matrix isolation method [4],

b Buried under the R-branch of very strong CO stretching band centered at 1033

cm" 1 [3].

c Frequency in the liquid state (Raman). It is also possible to assign this vibration

to a very weak infrared band at 1230 cm-1

. However, the latter assignment is not consistent with those of related compounds.

d See References [ 2] and [5].

References

[1] R.

[2] IR.

[3] IR.

[4] IR.

[5] IR.Th.

[6] Th.

[7] IR.

[8] Th.

[9] IR.Th.

J. R. Nielsen and N. E. Ward, J. Chem. Phys. 10, 81 (1942). G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand,

New York, 1945). C. Tanaka, K. Kuratani, and S. Mizushima, Spectrochim. Acta 9, 265 (1957). M. Van Thiel, E. D. Becker, and G. C. Pimentel, J. Chem. Phys. 27, 95 (1957). D. G. Burkhard and D. M. Dennison, J. Mol Spectr. 3, 299 (1959). M. Margottin-Maclou, J. Phys. Radium 21, 634 (1960). M. Falk and E. Whalley, J. Chem. Phys. 34, 1554 (1961) and references cited there. G. Zerbi, J. Overend, and B. Crawford, J. Chem. Phys. 38, 122 (1963). C. Tanaka and T. Shimanouchi, unpublished.

19
Molecule: Methanol CH3OH (liquid)

No. 22

Symmetry Cs Symmetry number = 1

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ l cm~ l a V\ OH stretch. 3328 D 3328 vb 3270-3480

v2 CH3 deg. stretch. 2980 C 2980 M 2993 (3)

Vj. CH3 sym. stretch. 2834 C 2834 S 2834(10)

Va CH3 deg. deform. 1480 C 1480 M 1464 (5b) OV(r,0). v5 CH3 sym. deform. 1450 C 1450 M 1464 (5b)

va OH bend. 1418 C 1418 M,b

Vl Chf) rock. 1115 C 1115 M 1107 (2) Vh C-0 stretch. 1030 C 1030 VS 1033 (6) a" Vy CH3 deg. stretch. 2946 C 2946 S 2940 (9) Vu) CH3 deg. deform. 1480 C 1480 M 1464 (5b) OVM.

Vu CH3 rock. 1165 C 1165(1)

V\2 C-0 torsion 655 D 655 vb

References

[1] R.

[2] R.

[3] IR.

[4] IR.Th.

S. Mizushima, Y. Morino, and G. Okamoto, Bull Chem. Soc. Japan 11, 698 (1936). G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand,

New York, 1945). M. Falk and E. Whalley, J. Chem. Phys. 34, 1554 (1961) and references cited there. C. Tanaka and T. Shimanouchi, unpublished.

20
Molecule: Methanol-di CH.jOD (gas)

No, 23

Symmetry Cs Symmetry number = 1

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm -1 cm~ l

a' V\ OD stretch. 2718 A 2718 M

CH3 deg. stretch. 3005 C 3000 M SFl^ of

CH3 OH).

v3 CH3 sym. stretch. 2843 A 2843 S

V4 CH3 deg. deform. 1473 B 1473 M OV(*,o). V5 CH3 sym. deform. 1456 A 1456 M

V6 OD bend. 864 A 864 S

V7 CH3 rock. 1230 B 1230 W

Vh CO stretch. 1040 A 1040 VS

n a Vi, CH3 deg. stretch. 2965 C 2960 S SF^ of

CH3 OH).

Vio CH3 deg. deform. 1473 B 1473 M OVN.

Vu CH3 rock. 1160 C 1160 VW

Vri C-0 torsion 213 E CF[2, 4]

References

[1] IR. G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand,

New York, 1945).

[2] IR. C. Tanaka, K. Kuratani, and S. Mizushima, Spectrochim. Acta 9, 265 (1957).

[3] Th. M. Margottin-Maclou, J. Phys. Radium 21 , 634 (1960).

[4] IR. M. Falk and E. Whalley, J. Chem. Phys. 34, 1554 ( 1961) and references cited there.

[5] Th. G. Zerbi, J. Overend, and B. Crawford, Jr., J. Chem. Phys. 38, 122 (1963).

[6] IR.Th. C. Tanaka and T. Shimanouchi, unpublished.

21

217-094 0-67-4
Molecule: Methanol-di CH3OD (liquid)

No. 24

Symmetry Cs Symmetry number = 1

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ l cm~ l

a' V\ OD stretch. 2467 D 2467 vb 2420-2560

v-l CH3 deg. stretch. 2978 C 2978 M 2992 (3) V3 CH3 sym. stretch. 2838 C 2838 S 2834(10)

V4 CH3 deg. deform. 1469 C 1469 M 1463 (5b) OV(no).

Vs CHj sym. deform. 1449 C 1449 M 1463 (5b) v6 OD bend. 940 C 940 M,b 955(1)

V7 CH3 rock. 1231 C 1231 W 1226(0)

VH CO stretch. 1038 C 1038 VS 1029 (6)

n a Vi, CH3 deg. stretch. 2951 C 2951 S 2943 (9) VlO CH3 deg. deform. 1469 C 1469 M 1463 (5b) OV(r4 ). Vu CHj rock. 1163 C 1163(1)

Viz C-O torsion 475 D 475 vb

References

[1] R.

[2] R.

[3] IR.R.

[4] IR.Th.

S. Mizushima, Y. Morino, and G. Okamoto, Bull, Chem. Soc. Japan 11, 698 (1936). G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand,

New York, 1945). M. Falk and E. Whalley, J. Chem. Phys. 34, 1554 (1961) and references cited there C. Tanaka and T. Shimanouchi, unpublished.

22
No. 25

Molecule: Methanol-d.3 CD3OH (gas)

Symmetry Cs Symmetry number = 1

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm -1 cm~ l

a' V\ OH stretch. 3690 D 3690 S

v2 CD3 deg. stretch. 2260 E

a 2260 M,sh

Vi CD3 sym. stretch. 2077 C 2077 S

V* CD.) deg. deform. 1047 D 1047 W

v3 CD3 sym. deform. 1134 C 1134 VS

J'W OH bend. 1297 C 1297 VS

V7 CD.) rock. 858 C 858 M

I'M CO stretch. 988 C 988 VS

a" v» CD., deg. stretch. 2235 D 2235 S

J'lO CD3 deg. deform. 1075 C 1075 W

VII CDs rock. 877 D 877 M

V\L C-0 torsion 256 E CF [1, 3].

a The value used by Margottin-Maclou for her normal coordinate treatment. References

[1] Th. M. Margottin-Maclou, J. Phys. Radium 21, 634 (1960).

[2] IR. M. Falk and E. Whalley, J. Chem. Phys. 34, 1554 (1961) and references cited there.

[3] Th. G. Zerbi, J. Overend, and B. Crawford, Jr., J. Chem. Phys. 38, 122 (1963).

[4] Th. C. Tanaka and T. Shimanouchi, unpublished.

No

Molecule: Methanol-cZ3 CD3OH (liquid)

Symmetry Cs Symmetry number = 1

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ l cm~ 1

a' V, OH stretch. 3310 D 3310 S,vb 3350 W,vb

Vi CD3 deg. stretch. 2235 D

a 2235 M 2230 M,dp

V3 CD3 sym. stretch. 2078 C 2078 S 2074 VS,p

V4 CD3 deg. deform. 1069 C 1069 W 1072 M,dp OV(i',o). V3 CD3 sym. deform. 1122 C 1122 VS 1127 M,p

n OH bend. 1391 C 1391 S,b 1360 VW,vb

V7 CD3 rock. 882 C 882 M 894 M,dp OV(r'n).

Vh CO stretch. 982 C 982 VS 986 VS,p

a" I'd CD3 deg. stretch. 2213 D

a2213 M 2213 VW

I'm CD3 deg. deform. 1069 C 1069 W 1072 M,dp OV(v4). Vn CDs rock. 882 D 882 M 894 M,dp OV(v7 ). Vu C-0 torsion 665 D 665 S,vb

a The value obtained in the vitreous solid (— 180 °C).

References

[1] IR.R. M. Falk and E. Whalley, J. Chem. Phys. 34, 1554 (1961) and references cited there.

[2] Th. C. Tanaka and T. Shimanouchi, unpublished.

23
Molecule: Methanol-ffi CD3 OD (gas)

No. 27

Symmetry Cs Symmetry number = 1

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm-1 cm~ x

a V\ OD stretch. 2724 D 2724 S

Vz CD3 deg. stretch. 2260 E

a2260 SF)^ of

CD3 OH).

v3 CD3 sym. stretch. 2080 C 2080 S

V4 CD3 deg. deform. 1024 D 1024 W

(vi, v6). V5 CD3 sym. deform. 1135 C 1135 VS

v6 OD bend. (v4 , v7 ) 1060 D 1060 W

Vi CD3 rock. (v6) 776 C 776 S

Vh CO stretch. 983 C 983 VS

a' Vi, CD3 deg. stretch. 2228 D 2228 S

V,0 CD3 deg. deform. 1080 C 1080 W

vu CD3 rock. 892 C 892. W

V\2 C-0 torsion 196 E CF[1, 3)

a The value used by Margottin-Maclou for her normal coordinate treatment.

References

[1] Th. M. Margottin-Maclou, J. Phys. Radium 21, 634 (1960).

[2] IR. M. Falk and E. Whalley. J. Chem. Phys. 34, 1554 (1961).

[3] Th. C. Tanaka and T. Shimanouchi, unpublished.

24
Molecule: Tetrafluoroethylene CF2 CF2

No. 28

Symmetry D2h Symmetry number =4

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ l cm~ l

dg V\ CC stretch. 1872 C ia 1872 M,p

V-l CF2 sym. stretch. 778 C ia 777.9 S,p

V3 CF2 scissors 394 C ia 394 W,p

CLu V4 CF2 twist. 190 E ia ia OC [3]. big V3 CF2 anti, stretch. 1340 D ia 1340 VW

V6 CF2 rock. 551 D ia 551 M

(liquid) biu V7 CF2 wag. 406 C 406 S ia big Vs CF2 wag. 508 D ia 508 S

(liquid)

b-iu Vg CF2 anti, stretch. 1337 C 1337 S ia Vio CF2 rock. 218 C 218 S ia b^u Vn CF2 sym. stretch. 1186 C 1186 S ia Vii CF2 scissors 558 C 558 S ia

References

[1] IR.R. J. R. Nielsen, H. H. Claassen, and D. C. Smith, J. Chem. Phys. 18, 812 (1950).

[2] R. A. Monfils and J. Duchesne, J. Chem. Phys. 18, 1415 (1950).

[3] IR. D. E. Mann, N. Acquista, and E. K. Plyler, J. Res. NBS 52,67 (1954) RP2474.

25
Molecule: Tetrachloroethylene CCI2CCI2

No. 29

Symmetry D2h Symmetry number = 4

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ x cm~ x (Liquid) (Liquid)

«</ V\ CC stretch. 1571 D ia 1571 (7)p

Vz CC12 sym. stretch. 447 D ia 447 (10)p

Vz CCI2 scissors 237 D ia 237 (7)p Uu V4 CCI2 twist. 110 E ia ia OC(2^ = 218X1],

b\g Vh CCI2 anti, stretch. 1000 D ia 1000 (0) vK CCI2 rock. 347 D ia 347 (4)dp

b\

u

v7 CCI2 wag. 288 D 288 M ia

b'Zg Vh CC12 wag. 512 D ia 512 (4)dp

b-zu V<> CCI2 anti, stretch. 908 C 908 S ia (CS2 soln.)

CCI2 rock. 176 C 176 S ia

b:\ u Vi\ CCI2 sym. stretch. 777 C 777 S ia (CS2 soln.)

Viz CCI2 scissors 310 C 310 W ia

References

[1] IR. D. E. Mann, N. Acquista, and E. K. Plyler, J. Res. NBS 52, 67 (1954) RP2474.

[2] IR. D. E. Mann, J. H. Meal and E. K. Plyler, J. Chem. Phys. 24, 1018 (1956).

[3] IR.R. G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand,

New York, 1945) and references cited there.

26
No. 30

Molecule: Tetrabromoethylene CBr2 CBr2 Symmetry D2h Symmetry number = 4

Sym.

class No.

Approximate

! type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ l cm~ l (Liquid) (Liquid)

ag Vi CC stretch. 1535 E ia (1547 (2)p

[1515 (l)p

FR(2r») [1].

v2 CBr2 sym. stretch. 265 D ia 265 (10)p v3 CBr2 scissors 144 D ia 144 (l)p

dll v4 CBr2 twist. 66 E ia ia OC [2], big Vs CBr2 anti, stretch. 880 D ia 880 (l)dp V6 CBr2 rock. 208 D ia 208 (2)dp

bm V7 CBr2 wag. 245 C 245 S ia

b-Zg Vh CBr2 wag. 464 D ia 464 (l)dp

bzu Vd CBr2 anti, stretch. 766 C 766 S ia Vio CBr2 rock. 119 C 119 M ia b3u I'll CBr2 sym. stretch. 635 C 635 S ia

Vvz CBr2 scissors 188 C 188 M ia

References

[1] R. F. E. Malherbe, G. Allen and H. J. Bernstein, Can. J. Chem. 31, 1223 (1953).

[2] IR. D. E. Mann, J. H. Meal, and E. K. Plyler, J. Chem. Phys. 24, 1018 (1956).

No. 31

Molecule: 1,1-Difluoro 2,2-dichloroethylene CF2 CC12 Symmetry C2v Symmetry number= 2

Sym.

class No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ l cm~ l (Gas) (Liquid)

ai t'l CC stretch. 1749 B 1749 VS 1738.8 S

V2 CF stretch. 1032 B 1032 VS 1027.6 M

v3 CC1 stretch. 622 C 622 M 623.0 S

Vi CF2 scissors 434 C 434 433.8 VS

Vs CC12 scissors 258 C 258 S 258 VS

a-z V6 Torsion 167 D 167 VVW

b\ Vv CF stretch. 1327 B 1328 VS 1313 VVW

Vh CC1 stretch. 989 B 989 VS 986 VW

Vh CF2 rock. 459 C 459 VW 454 W

t'lO CC12 rock. 192 C 192 187.8 W

bz I'll CF2 wag. 564 C 564 S 560.8 VS

Vl2 CC12 wag. 323 C 323 W

References

[1] IR.R. J. R. Nielsen and H. H. Claassen, J. Chem. Phys. 18,485(1950).

[2] IR. D. E. Mann and E. K. Plyler, J. Chem. Phys. 23, 1989 (1955).

[3] Th. D. E. Mann, L. Fano, J. H. Meal, and T. Shimanouchi, J. Chem. Phys. 27, 51 (1957).

27
Molecule: trems-Difluorodichloroethylene CFC1CFC1

No. 32

Symmetry C2h Symmetry number = 2

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm -1 cm -1 (Gas) (Liquid)

CLg V\ CC stretch. 1707 C ia 1707 VS,p

v-z CF stretch. 1186 C ia 1186 W,p

V3 CC1 stretch. 632 C ia 632 M,p

V\ CF bend. 425 C ia 425 M,p

Vs CC1 bend. 288 C ia 288 M,p

Ou Vs CFC1 wag. 333 C 333 M ia

1'7 Torsion 140 D ia CF [2], by Vh CFC1 wag. 529 C ia 529 M,dp

11214 VS

bu Vy CF stretch. 1190 E

[1167 VS

ia FK(i* + I'm).

v, 0 CC1 stretch. 892 B 892 VS ia Vn CF bend. 426 C ia Vl2 CC1 bend. 175 C 175 M ia

References

[1] IR.R. D. E. Mann and E. K. Plyler, J. Chem. Phys. 26, 773 (1957).

[2] Th. D. E. Mann, L. Fano, J. H. Meal, and T. Shimanouchi, J. Chem. Phys. 27, 51 (1957).

28
No. 33

Molecule: Hexafluoroethane CF3CF3

Symmetry D3(1 Symmetry number = 6

Sym.

class No.

...

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm _l cm*'

(Gas) (Gas)

«;/ v\ CC stretch. 1228 D ia 1228 OC.a

V-l CF.t sym. stretch. 807 C ia 807 VS,p

V:\ CF:) sym. deform. 348 C ia 348 W,p

«1H Va Torsion 67 D ia ia ( b

) Uiu P-i CF.-t sym. stretch. 1117 B 1117 VS ia n CFi sym. deform. 714 B 714 VS ia

e<i I'V CF3 deg. stretch. 1243 C ia 1250 VW,dp

Vh CF3 deg. deform. 619 C ia 619 W,dp

Vh CF3 rock. 376 C ia 372 W,dp

e„ V\D CF3 deg. stretch. 1251 B 1251 VS ia

V\\ CF3 deg. deform. 523 C 520 S ia

V\1 CF.t rock. 220 C 220S ia

a The mean value of frequencies obtained from six combination bands.

h Obtained from thermodynamic data [3]. References

[1] IR.R. R. A. Carney, E. A. Piotrowski, A. G. Meister, J. H. Broun, and F. F. Cleveland, J. Mol. Spectr. 7, 209 (1961).

[2] Th. T. Fujiyama and T. Shimanouchi, unpublished.

[3] D. E. Mann and E. K. Plyler, J. Chem. Phys. 21, 1116 (1953).

29
No. 34

Molecule: Hexachloroethane CCI3CCI3

Symmetry D3d Symmetry number = 6

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm

~ 1 cm~ 1

(Solid) (Solid)

dig p\ CC stretch. 975 C ia 975 VW,p

p-i CCI3 sym. stretch. 431 C ia 431 VS,p

P* CCI3 sym. deform. 170 C ia 170 W

a | M P4 Torsion 61 D ia ia OC.a

a-iu Vh CCI3 sym. stretch. 675 C 675 S ia Pg CCI3 sym. deform. 372 C 372 S ia ?g Pi CCI3 deg. stretch. 859 C ia 859 W

Ph CCI3 deg. deform. 340 C ia 340 M

Pg CCI3 rock. 223 C ia 223 S

e„ PH) CCI3 deg. stretch. 778 C 778 VS ia Pn CCI3 deg. deform. 271 C 271 S ia Pvz CCI3 rock. 114 C 114 W ia

a Obtained from p7 + p^ and p* + p4 .

References

[1] IR.R.Th. T. Fujiyama and T. Shimanouchi, unpublished.

[2] IR.R. R. A. Carney, E. A. Piotrowski, A. G. Meister, J. H. Broun, and F. F. Cleveland,

J. Mol. Spectr. 7 , 209 (1961).

30
Molecule: Hexabromoethane CBr3CBr3

No. 35

Symmetry D3 d Symmetry number = 6

Sym.

class No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm

~ 1 cm~'

(Solid) (Solid)

dig Vy CC stretch. 940 C ia 940 M

Vt CBr.-j sym. stretch. 255 C ia 255 VS,p

V3 CBr3 sym. deform. 120 C ia 120 W

dll

Va Torsion 51 D ia ia OC.a

d-2u CBr:i sym. stretch. 559 C 559 S ia CBr3 sym. deform. 254 C 254 S ia ^7 CBr3 deg. stretch. 768 C ia 768 M,dp

Vn CBr3 deg. deform. 204 C ia 204 S,dp

Vn CBr3 rock. 139 C ia 139 M

e„ V 10 CBr3 deg. stretch. 656 C 656 VS ia

Pll CBr3 deg. deform. 168 C 168 S ia Vl2 CBr3 rock. 82 C 82 M ia

a Obtained from v1 -I- tq and v* + v*.

References

[1] IR.R.Th. T. Fujiyama and T. Shimanouchi, unpublished.

[2] IR.R. R. A. Carney, E. A. Fiotrowski, A. G. Meister, J. H. Broun, and F. F. Cleveland,

J. Mol. Spectr. 7 , 209 (1961).

31
Molecule: Ethylene CH2CH2

No. 36

Symmetry D2h Symmetry number =4

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm -

1

cm~'

(ly V\ CH2 sym. stretch. 3026 B ia 3026.4 (10)p

Vz CC stretch. 1623 D ia 1622.6 (8)p FR(2i' l „).

V-i CH2 scissors 1342 B ia 1342.2 (10)p au *0 CH2 twist. 1023 E ia ia OCfio + *>«)[4]. C5 CH2 anti, stretch. 3103 B ia 3102.5 (l)dp

J'B CH2 rock. 1236 C ia 1236 (l)dp

(liquid)

b\„ v7 CH2 wag. 949 A 949.3 M ia

b-iy V* CH2 wag. 943 C ia 943 (l)dp

(liquid)

b-zu CH2 anti, stretch. 3106 B 3105.5 S ia *9o CH2 rock. 826 A 826.0 W ia bzu I'll CH2 sym. stretch. 2989 A 2988.66 S ia *02 CH2 scissors 1444 B 1443.5 S ia

References

[1] R. H. Rank, E. R. Shull, and D. W. E. Axford, J. Chem. Phys. 18, 116 (1950).

[2] R. T. Feldman, J. Romanko, and H. L. Welsh, Can. J. Phys. 34, 737 (1956).

[3] IR. H. C. Allen, Jr., and E. K. Plyler, J. Am. Chem. Soc. 80, 2673 (1958).

[4] IR. W. L. Smith and I. M. Mills, J. Chem. Phys. 40, 2095 (1963).

[5] IR. R. L. Arnett and B. L. Crawford, Jr., J. Chem. Phys. 18, 118 (1950).

[6] IR.R. G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand,

New York, 1945).

[7] IR. D. A. Dows, J. Chem. Phys. 36, 2833 (1962).

32
Molecule: 1 ,2-Dichloroethane CH2 CICH2 CI

(trans form)

No. 37

Symmetry C2h Symmetry number — 2

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ 1 cm*'

(Liquid)

a„ V\ CH2 sym. stretch. 2957 D ia 2957 (10)p

Vz CH2 scissors 1445 C ia 1445 (4b)dp

v* CH2 wag. 1304 C ia 1304 (6)p

CC stretch. 1052 C ia 1052 (4)p

V:-, CC1 stretch. 754 C ia 754 ( 10b)p

Vk CCC1 deform. 300 C ia 300 (8)p au Vi CH2 anti, stretch. 3005 D 3005 W ia SF(gauche p t . (liquid) gauche V\ 1 ). Vh CH2 twist. 1123 B 1122.5 W ia P» CH2 rock. 773 B 772.5 M ia Put Torsion. 123 C

a

1 23 M ia b. Pn CH2 anti, stretch. 3005 D ia 3005 (8b)dp

« P\ 2 CH2 twist. 1264 C ia 1264 (3)dp

V\:\ CH2 rock. 989 C ia 989 (2)p

b„ I'm CH2 sym. stretch. 2983 C 2983.3 M ia

P\:> CH2 scissors 1461 A 1460.6 S ia PlH CH2 wag. 1232 B 1232.3 S ia

V\l CC1 stretch. 728 C 728.3 VS ia VlH CCC1 deform. 222 C 222.3 W ia

a Torsional vibration appears at 134 cm 1 in the liquid state.

References

[1] IR.R.

[2] IR.R.

[3] IR.R.

[4] IR.R.

[5] Th.

[6] IR.

[7] IR.

G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand,

New York, 1945) and references cited there.

S. Mizushima, Y. Morino, I. Watanabe, T. Shimanouchi, and S. Yamaguchi, J. Chem.

Phys. 17, 591 (1949). John T. Neu and Wm. D. Gwinn, J. Chem. Phys. 18, 1642 (1950).

J. K. Brown and N. Sheppard, Trans. Faraday Soc. 48, 128 (1952).

I. Nakagawa and S. Mizushima, J. Chem. Phys. 21, 2195 (1953).

I. Ichishima, H. Kamiyama, T. Shimanouchi, and S. Mizushima, J. Chem. Phys. 29,

1190 (1958). S. Mizushima, T. Shimanouchi, I. Ichishima and H. Kamiyama, Revue Universelle des Mines 15 , 447 (1959).

33
Molecule: 1,2-Dichloroethane CH2 CICH2CI

(gauche form)

No. 38

Symmetry C2 Symmetry number =2

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ x cm~ l (Liquid) a CH2 anti, stretch. 3005 D 3005 W 3005 (8b)dp SF(^,,,

(liquid) trans v7 ). V% CH2 sym. stretch. 2957 D 2957 M 2957 (10)p SF (trans v\.

(liquid) trans I'm).

V?, CH2 scissors 1433 C 1433 M 1429 (6)dp SF (^, 3 ). (liquid)

Va, CH2 wag. 1315 C 1315 W 1304 (6) Vh CH2 twist. 1207 C 1207 (5)p

V* CC stretch. 1027 D 1027 W 1031 (2)dp

V7 CH2 rock. 948 B 947.7 M 943 (5)p

Vh CC1 stretch. 669 C 669 M 654 (8)p

CCC1 deform. 272 D 272 VW 265 (5)p

(liquid)

V\o Torsion 125 (5b)

b V11 CH2 anti, stretch. 3005 D 3005 W 3005 (8b)dp SF (1/

1 , (liquid) trans vt). vn CH2 sym. stretch. 2957 C 2957.2 W

*^13 CH2 scissors 1436 B 1436.3 W

V U CH2 wag. 1292 B 1292.1 S

t’lo CH2 twist. 1146 D 1146 VW 1145 (3)dp

t'lfi CH2 rock. 890 B 890.3 M 881 (4)dp

CC1 stretch. 693 B 692.5 W 677 (6b)dp

rin CCC1 deform. 410 C 409.6 M 411 (5)dp

See references for the trans form.

34
Molecule: 1,2-Dibromoethane CH2 BrCH2 Br

(trans form)

No. 39

Symmetry C2 h Symmetry number = 2

Sym.

class No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ x cm~ l (Liquid) (Liquid)

V\ CH2 sym. stretch. 2972 D ia 2972 (10)p

v-i CH2 scissors 1449 C ia 1440 (5)dp

r.t CH2 wag. 1255 C ia 1255 (10b)p SF(t', 2 ). V* CC stretch. 1053 C ia 1053 (9)dp

CBr stretch. 660 C ia 660 (10b)p

r« CCBr deform. 190 C ia 190 (10)p

Q-u r7 CH2 anti, stretch. 3037 D 3037 S ia Vh CH2 twist. 1087 C 1087 M ia Vh CH2 rock. 753 C 753 S ia rui Torsion 118 D

a

1 18 132 (0) (gas) rn CH2 anti, stretch. 3013 D ia 3013 (4b)dp

CH2 twist. 1255 C ia 1255 (10b )p SF(r3 ). Vis CH2 rock. 933 C ia 933 (2)p

bu rM CH2 sym. stretch. 2974 D 2974 S ia

ri.-, CH2 scissors 1441 D 1441 M ia CH2 wag. 1186 C 1186 VS 1186 (0) V\1 CBr stretch. 589 C 589 S ia Vis CCBr deform. 193 D 193 ia

a Torsional frequency in the liquid state was observed at 127 cm' 1

.

References

[1] IR.R. S. Mizushima, Y. Morino, I. Watanabe, T. Shimanouchi and S. Yamaguchi, J. Chem.

Phys. 17, 591 (1949).

[2] IR.R. John T. Neu and Wm. D. Gwinn, J. Chem. Phys. 18, 1642 (1950).

[3] IR.R. J. K. Brown and N. Sheppard, Trans. Faraday Soc. 48, 128 (1952).

[4] IR. I. Ichishima, H. Kamiyama, T. Shimanouchi and S. Mizushima, J. Chem. Phys. 29,

1190(1958).

35

»
Molecule: 1,2-Dibromoethane CH2 BrCH2 Br

(gauche form)

No. 40

Symmetry C2 Symmetry number=2

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ l cm ~ 1 (Liquid) (Liquid) a V\ CH2 anti, stretch. 3005 D 3005 (5) SF(i/,,). v2 CH2 sym. stretch. 2953 D 2953 VS 2953 (8)p SF(j/12 ). v2 CH2 scissors 1420 C 1420 M 1419 (3)dp SF(vis).

V4 CH2 wag. 1278 C 1278 M 1276 (3) Vs CH2 twist. 1104 C 1104 W 1104 (l)dp SF(rl5 ).

Vfi CG stretch. 1019 C 1019 M 1019 (1) V7 CH2 rock. 898 C 898 M 899 (3)p

Vh CBr stretch. 550 C 550 M 551 (8) v» CCBr deform. 231 C 231 (3)p

Vw Torsion 91 (2b)dp

b I'll CH2 anti, stretch. 3005 D 3005 (5) SF(i^i).

Vi-1 CH2 sym. stretch. 2953 D 2953 VS 2953 (8)p SF(r2). Vis CH2 scissors 1420 C 1420 M 1419 (3)dp SYM.

V1 4 CH2 wag. 1245 C 1245 S 1243 (1) ^15 CH2 twist. 1104 C 1104 W 1104 (l)dp SF(u5 ). V lfi CH2 rock. 836 C 836 S 836 (2)dp

Vn CBr stretch. 589 C 589 S 583 (6b)dp

V 1

H

CCBr deform. 355 C 355 355 (5)dp

See references for the trans form.
No. 41

Molecule: 1 ,2-Chlorobromoethane CtbCICHLBr

(trans form)

Symmetry Cs Symmetry number= 1

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm ~ 1 cm~ l

(Solid) (Liquid)

t a P\ CH2 sym. stretch. 2960 D 2960 (lOvb) SF(r2 ,gauche

r3 , gauche

p4 ). V2 CH2 sym. stretch. 2960 D 2960 (lOvb) SF(ri, gauche

r3 , gauche

p4 ). r3 CH2 scissors 1446 D 1446 S

Pi CH2 scissors 1444 C 1444 (3b) r5 CH2 wag. 1284 C 1284 M 1284 (7)p r6 CH2 wag. 1203 C 1203 S 1203 (3) Vl CC stretch. 1052 C 1056 M 1052 (4)dp

V» CC1 stretch. (r9 ) 726 C 722 S 726 (10b)p

r9 CBr stretch. (r8 ) 630 C 630 S 630 (9) Pio CCC1 deform, (rn) 251 C 251 (10)p SF(gauche

Pn). rn CCBr deform. (r)0 ) 202 C 202.0 210 (2b)

(CCL,

soln.) a" Pl2 CH2 anti, stretch. 3010 D 3010 (3vb) SF(r13 , gauche r,. gauche r2 ). ri3 CH2 anti, stretch. 3010 D 3010 (3vb) SF(ri 2 , gauche r,. gauche r2 ). V\i CH2 twist. 1259 C 1258 VW 1259 (3) ris rCH2 twist. 1111 D 1111 M

ri6 CH2 rock. 961 C 961 VW 961 (lb)

ri7 CH2 rock. 763 D 763 M

Pis Torsion 123 C 123.0

(CCL,

soln.)

References

[1] R. S. Mizushima, Y. Morino, Y. Miyahara, and M. Tomura, Sci. Pop. Inst. Physic. Chem.

Res. Japan 39, 387 (1942).

[2] IR.R. J. K. Brown and N. Sheppard, Trans. Faraday Soc. 48, 128 (1952).

[3] IR. L. R. Blaine, J. Res. NBS 67C (Engr. and Instr.) No. 3, 207 (1963).

37
Molecule: 1 ,2-Chlorobromoethane CHUCICFhBr

(gauche form)

No. 42

Symmetry Ci Symmetry number = 1

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ x cm~ l (Liquid) (Liquid)

V, CH2 anti, stretch. 3010 D 3010 (3vb) SF(r>2 , trans

v\ 2 , trans

Vis). V2 CH2 anti, stretch. 3010 D 3010 (3vb) SFfr'i, trans

vi2 , trans ^13 ). V3 CH2 sym. stretch. 2960 D 2960 (lOvb) SF)^, trans Vu trans v2 ). V4 CH2 sym. stretch. 2960 D 2960 (lOvb) SF(v3 , trans

V\, trans v2). Vs CH2 scissors 1428 D 1428 S 1421 (3b) SF(v6 ).

Vfi CH2 scissors 1428 D 1428 S 1421 (3b) SF(i/5). V7 CH2 wag. 1299 C 1299 S 1299 (1) Vh CH2 wag. 1260 C 1260 S 1259 (3) Vs CH2 twist. 1190 D 1190 M 1189 (2)p

Vio CH2 twist. 1127 C 1127 M 1128 (l)dp

Vn CC stretch. 1025 C 1025 M 1023 (1) Vl2 CH2 rock. 923 C 923 S 919 (3)p

V\3 CH2 rock. 856 C 856 S 852 (2) V\4 CC1 stretch. (v, 5 ) 664 C 664 S 665 (6) V\s CBr stretch. (ri 4 ) 571 C 571 S 568 (9)p

V\6 CCC1 deform. (vx7 ) 385 C 385 (3)dp

Vl7 CCBr deform, (t^s) 251 D 251 (10) SF(trans vm).

V,H Torsion 107 D 107 (2b)

See references for the trans form.

38
Molecule: Ethyl floride CH3CH2 F

No. 43

Symmetry Cs Symmetry number = 1

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm - 1 cm -1

(Liquid)

a' *9 CH3 deg. stretch. 3003 D 3003 VS 2986 VS,dp OV(l92,I9 3 ). *9 CH2 sym. stretch. 2941 D 2941 2941 VS,p

V3 CH3 sym. stretch. 2915 D 2915 S 2921 M

*9 CH2 scissors 1479 C 1479 M 1480 W,b,dp

Vf> CH3 deg. deform. 1449 D 1449 S 1458 M,b,dp OV(rH). Va CH3 sym. deform. 1395 C 1395 S 1393 W,p

*9 CH2 wag. 1365 D 1365 M 1365 VW

(liquid)

Vh CH3 rock. 1108 C 1108 VS 1103 S,p

Vi> CC stretch. 1048 D 1048 VS 1041 M,b,dp

*9o CF stretch. 880 B 880 VS 873 VS,p

*9i CCF deform. 415 C 415 419 W,p

n a *92 CH2 anti, stretch. 3003 D 3003 VS 2986 VS,dp OV(*/| ,^ 13 ). *93 CH3 deg. stretch. 3003 D 3003 VS 2986 VS,dp OV(i/| ,*' l2 ). *94 CIL deg. deform. 1449 D 1449 S 1458 M,b,dp OV(.*).

*95 CH2 twist. 1277 C 1277 1276 W,b,dp

*9fi CH3 rock. 1048 D 1048 VS 1041 M,b,dp OVlt'o).

V|7 CH2 rock. 810 C 810 W 815 VW

*9 H Torsion 243 B 242.7

References

[1] IR.R. D. C. Smith, R. A. Saunders, J. Rud Nielsen, and E. E. Ferguson, J. Chem. Phys.

20, 847 (1952).

[2] IR. E. Catalano arid K. S. Pitzer, J. Phys. Chem. 62, 873 (1958).

[3] IR. G. Sage and W. Klemperer, J. Chem. Phys. 39, 371 (1963).

39
Molecule: Ethyl chloride CH3CH2 C1

No. 44

Symmetry Cs Symmetry number = 1

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm -1 cm~ l (Liquid)

a' V\ CH3 deg. stretch. 2983 D 2983 S 2966 (10)p V2 CH2 sym. stretch. 2946 B 2945.8 S 2933 (10)p v3 CH3 sym. stretch. 2890 D 2890 S 2880 (4)p v4 CH2 scissors 1452 D 1452 VS 1452 (2)p OV(i/5 ,rH).

V-D CH3 deg. deform. 1452 D 1452 VS 1452 (2)p OV(r4,i'i4). V6 CR, sym. deform. 1383 C 1383 VS 1380

v7 CH2 wag. 1287 C 1287 VS 1280

Vs CH3 rock. 1080 D 1080 W 1072 (l)p

Vy CC stretch. 972 D 972 VS 970 (lb)p

Vio CC1 stretch. 676 B 676 VS 658 (8)p

I'll CCC1 deform. 336 B 336 VS 335 (2)p

n a V\2 CH2 anti, stretch. 3012 D 3012 S 3020 (7)dp

Vl 3 CH3 deg. stretch. 2983 D 2983 S 2983 (7)dp

Vl4 CH3 deg. deform. 1452 D 1452 VS 1452 (2)p OV(r4 ,r5 ). Vl5 CH2 twist. 1244 E 1244

Vl6 CH3 rock. 972 D 972 VS 970 (l)p OV(r>9 ). Vn CH2 rock. 785 A 785.1 M

Vis Torsion 243 B 243 W

References

[1] IR.R. L. W. Daasch, C. Y. Liang, and J. Rud Nielsen, J. Chem. Phys. 22, 1293 (1954).

[2] R. G. Allen and H. J. Bernstein, Can. J. Chem. 32, 1124 (1954).

[3] IR. R. N. Dixon, Spectrochim. Acta 9, 59 (1957).

[4] IR. W. G. Fateley and F. A. Miller, Spectrochim. Acta 17, 857(1961).

[5] IR. N. T. McDevitt, A. L. Rozek. F. F. Bentley, and A. D. Davidson. J. Chem. Phys.

42, 1173 (1965).

40
No. 45

Molecule: Ethyl bromide CH3 CH2 Br

Symmetry Cs Symmetry number = 1

Sym.

class No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm

l cm-1

(Liquid)

a' V\ CH3 deg. stretch. 2988 C 2988 S 2971 (2b)p OV(r,3 ). Vz CH2 sym. stretch. 2937 B 2936.5 S 2924 (2)p r3 CH3 sym. stretch. 2880 B 2879.8 S

CH2 scissors 1451 D 1451 M 1442 (2b)dp OV(i'5 ,ri 4 ).

Cr, CH3 deg. deform. 1451 D 1451 M 1442 (2b)dp OV(r'4 ,i'i 4 ). V6 CH3 sym. deform. 1386 B 1386 M

Vl CH2 wag. 1252 E

f 1258 VS

(1247 VS 1248 (2b)p FR(r9 + i'i i ). CH3 rock. 1061 D 1061 VW 1069 (l)p r9 CC stretch. 964 B 964 S 960 (lb)dp

Vio CBr stretch. 583 B 583 VS 560 (10)p

I'll CCBr deform. 290 B 290 S 293 (3)p a" ri2 CH2 anti, stretch. 3018 B 3018 S

ri3 CH3 deg. stretch. 2988 C 2988 S 2971 (2b)p OV(v,).

Pl4 CH3 deg. deform. 1451 D 1451 M 1442 (2b)dp

V\r> CH2 twist. 1248 E CF.

rie CH3 rock. 964 D 964 S 960 (lb)dp OV(rs ). Pl7 CH2 rock. 770 B 770 M

Vl» Torsion 247 B 247

Note. The CH2 twisting frequency, i'is, was calculated from the modified UreyBradley force constants which were transferred from hydrocarbons and halogenoethanes [5]. References

[1] R.

[2] R.

[3] IR.

[4] IR.

[5] IR.Th.

[6] IR.

J. Wagner, Zeit. Phys. Chem. B40, 439 (1938).

J. K. Brown and N. Sheppard, Trans. Faraday Soc. 50, 535 (1954). R. N. Dixon, Spectrochim. Acta 9, 59 (1957). N. T. McDevitt, A. L. Rozek, F. F. Bentley, and A. D. Davidson, J. Chem. Phys.

42, 1173 (1965). T. Shimanouchi and S. Takayama, unpublished.

S. Kinumaki and Y. Musha, unpublished.

41
Molecule: Ethane CH3CH3

No. 46

Symmetry D3d Symmetry number = 6

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm -1 cm~ l 12899.2 S,p

Cllg V\ CH3 sym. stretch. 2915 E ia 12955.1 S,p

FR(2r„).

v2 CH3 sym. deform. 1400 E ia OC [1, 2], V3 CC stretch. 993 A ia 993.0 S,p

U\u V4 Torsion. 275 D ia ia CF.a

a.2u Vs CH3 sym. stretch. 2915 E

12954.0 S

(2895.6 M

ia FR(i/8 + vu ).

V6 CH3 sym. deform. 1379 A 1379.2 W ia eu v7 CH3 deg. stretch. 2995 A 2995.5 M ia

Vh CH3 deg. deform. 1472 A 1472.2 S ia

Vi, CH3 rock. 822 A 821.52 S ia eg Vio CH3 deg. stretch. 2955 C ia 2963 W

(liquid)

Vu CH3 deg. deform. 1460 C ia 1460 M,dp

(liquid)

V\2 CH3 rock. 1190 E ia OC [1, 2].

a Calculated from specific heat data.

References

[1] IR.R. G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand,

New York, 1945) and references cited there.

[2] IR. L. G. Smith, J. Chem. Phys. 17, 139 (1949).

|3] IR. G. E. Hansen and D. M. Dennison, J. Chem. Phys. 20, 313 (1952).

42
Molecule: Ethane-de CD3CD3

No. 47

Symmetry D3d Symmetry number = 6

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm -1 cm -1

(Liquid)

dig V\ CD3 sym. stretch. 2100 E ia (2147 S

[2083 S

FR(2r„).

v2 CD3 sym. deform. 1158 C ia 1158 M

Vi CC stretch. 852 C ia 852 S

&\

V4 Torsion 200 D ia ia CF.a

d2u Vi CD3 sym. stretch. 2095 E

(2087.3 S

[2139.7

ia FR(i'h + l^n).

V6 CD3 sym. deform. 1077 A 1077 S ia V7 CD3 deg. stretch. 2236 A 2236 S ia Vh CD3 deg. deform. 1082 A 1082 S ia Vg CD3 rock. 594 A 593.7 S ia V\o CD3 deg. stretch. 2225 C ia 2225 S,b

I'll CD3 deg. deform. 1055 C ia 1055 M,b

V\2 CD3 rock. 970 C ia 970 W,b

a Calculated from specific heat data.

References

[1] IR.R. G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand,

New York, 1945) and references cited there.

[2] IR. G. E. Hansen and D. M. Dennison, J. Chem. Phys. 20, 313 (1952).

43
Molecule: Dimethylether CH3OCH3

No. 48

Symmetry C2 V Symmetry number = 2

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ l cm~ ] (Gas) (Liquid) a 1 V\ CH;t deg. stretch. 2996 B 2996 S 2989 S

Vz CH.( sym. stretch. 2817 B 2817 S 2815 VS,p

V-A CH j deg. deform. 1464 D 1464 M

Va CH.( sym. deform. 1452 D 1452 M 1452 S,dp

CH;i rock. 1244 B 1244 W

Vti CO sym. stretch. 928 B 928 S 922 S,p

Vi COC deform. 418 C 418 M 428 M,p

a-z VH CH.j deg. stretch. 2952 C ia 2952 S

v» CH3 deg. deform. 1464 D ia SF(i/3 ). Vm CHj rock. 1150 C ia 1150 M,d

I'll C-0 torsion 203 E ia CF [3J. 6 , Viz CH3 deg. stretch. 2996 B 2996 S 2989 S OV(iq).

V\A CH3 sym. stretch. 2817 B 2817 S 2815 VS,p OV(»A>).

Vu CH.i deg. deform. 1464 D 1464 M OV(v:i ). Vlo CH.t sym. deform. 1452 D 1452 M 1452 S,dp OV{v4 ). Vm CH3 rock. 1227 C 1227 W

Vn CO anti, stretch. 1102 B 1102 VS 1104 M,dp

bz VlH CH3 deg. stretch. 2925 B 2925 S

Vm CH3 deg. deform. 1464 D 1464 M OV(v:i ). Vzu CH3 rock. 1179 B 1179 VS 1170 sh

Vzi C-0 torsion 242 C 242 W 2

References

[1] IR.R. G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand,

New York, 1945).

[2] R. R. C. Taylor and G. L. Vidale, J. Chem. Phys. 26, 122 (1957).

[3] IR.R. Y. Kanazawa and K. Nukada, Bull. Chem. Soc. Japan 35 , 612 (1962).

[4] IR. W. G. Fateley and F. A. Miller, Spectrochim. Acta 18, 977 (1962).

[5] Th. T. Shimanouchi and M. Oka, unpublished.

44
Molecule: Dimethylether-d.3 CH3OCD3

No. 49

Symmetry Q Symmetry number = 1

Sym.

class No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ l cm~ l (Gas)

a' V\ CH3 deg. stretch. 2992 B 2992 S

v2 CH3 sym. stretch. 2819 B 2819 S

v-.i CD3 deg. stretch. 2244 B 2244 S

v4 CD3 sym. stretch. 2058 B 2058 S

vr, CH3 deg. deform. 1465 C 1465 M

V8 CH3 sym. deform. 1453 C 1453 M

V1 CH3 rock. 1212 B 1212 M

Vh CO anti, stretch. 1156 C 1156 VS

CD3 sym. deform. 1111 B 1111 S

V\o CD3 deg. deform. 1061 C 1061 M

Vu CD3 rock. 947 C 947 W

Vyz CO sym. stretch. 860 C 860 M

^13 COC deform. 395 E CF [2],

ft a ^14 CH3 deg. stretch. 2932 B 2932 S

P\r, CD3 deg. stretch. 2189 B 2189 S

Vui CH3 deg. deform. 1462 D 1462 M

V\7 CH3 rock. 1156 C 1156 VS OV(r>K ). VI

CD3 deg. deform. 1061 C 1061 M OV(n,„).

I'm CD3 rock. 901 C 901 W

V20 CH3

- 0 torsion 227 E CF [2], V2 \ CD3

- 0 torsion 164 E CF [2].

References

[f] IR. J. P. Perchard, Theses faculte des sciences de L’universite de "Paris (1962).

[2] Th. T. Shimanouchi and M. Oka, unpublished.

45
Molecule: Malononitrile NCCH2CN

No. 50

Symmetry C2V Symmetry number = 2

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ l cm -1

(Liquid) (Liquid)

Oi V\ CH2 sym. stretch. 2935 C 2935 VS 2929 (5) V2 C = N sym. stretch. 2275 C 2275 M 2263 (7) SF(r9 ). V3 CH2 scissors 1395 C 1395 VS 1386 (4) V4 CC sym. stretch. 890 C 890 S 892 (5) v5 CCC deform. 582 C 582 M 574 (3b) ve CCN bend. 167 C 167(10) a2 V7 CRi twist. 1220C 1220 VW 1214(3)

Vs CCN bend. 366 C

a371 M 367(10) SF(r12). Vs C = N anti, stretch. 2275 C 2275 M 2265 (7) SFfo).

ViO CH2 wag. 1318 C 1318 W 1310(2)

Vu CC anti, stretch. 982 C 982 S 975(1)

V\2 CCN bend. 366 C 366 S 367(10) SF(hO.

bz V\3 CH2 anti, stretch. 2968 C 2968 VS 2960(1)

V\4 CH2 rock. 933 C 933 M

*^15 CCN bend. 337 C 337 S

a Activated only in solid phase.

References

[1] IR.R.Th. T. Fujiyama and T. Shimanouchi, Spectrochim. Acta 20, 829 (1964).

[2] R. K. W. F. Kohlrausch and G. Prinz Ypsilanti, Zeits. Physik. Chemie B. 29, 274

(1934).

46
No. 51

Molecule: Malononitrile-cf2 NCCD2 CN

Symmetry C2v Symmetry number =2

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm

~ 1 cm~ 1

(Liquid) (D2 0 soln.) a i Vl CD2 sym. stretch. 2146 C 2146 S 2146 (4) v> C = N sym. stretch. 2272 C 2272 M 2273 (8) SF(r„).

V:\ CD-2 scissors 1037 C 1037 S 1033 (3) Va CC sym. stretch. 858 C 858 M 854 (5)

V:, CCC deform. 577 C 577 M 581 (2) Vh CCN bend. 163 C 163 (4) a> Vi CD2 twist. 892 C 892 VW 892 (1) V» CCN bend. 356 C 356 (4) SF(r> 2 ). 6. C = N anti, stretch. 2272 C 2272 M 2273 (8) SF(c2 ). (1142 M (1130 (0.5)

I'll) CD2 wag. 1153 C

1 1165 M 1 1162 (0.5) FR(c, 4 + Viz).

V 11 CC anti, stretch. 829 C 829 M 828 (1) Vvi CCN bend. 356 C 356 S 356 (4) SF(i'n). b> Vt:\ CD2 anti, stretch. 2230 C 2230 S 2228 (2) V\A CD2 rock. 795 C 795 W

V\:> CCN bend. 302 C 302 (1)

Reference

[1] IR.R.Th. T. Fujiyama and T. Shimanouchi, Spectrochim. Acta 20 , 829 (1964).

47
Molecule: Ethylcyanide CH3 CH2 CN

No. 52

Symmetry Cs Symmetry number = 1

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ l cm-1

(Liquid) [1] (Liquid) [1] a' V\ CH3 deg. stretch. 3001 C 3001 VS 2999 S OV(r14).

v-l CH2 sym. stretch. 2955 C 2955 VS 2949 VS,p

v3 CH3 sym. stretch. 2900 C 2900 S 2898 S,p

V4 C = N stretch. 2254 C 2254 VS 2251 VS,p

Vo CH3 deg. deform. 1465 C 1465 S 1466 VS,p SF(pie). V6 CH2 scissors 1433 C 1433 S 1436 M,p

Vi CH3 sym. deform. 1387 B 1387 M 1374 VW,p

Vs CH2 wag. 1319 B 1319 M 1322 W,p

Vs C — CN stretch. 1077 B 1077 S 1078 M,p

Vi0 CC stretch. 1005 B 1005 M 1010 S,p

Vu CH3 rock. 836 B 836 W 838 S,p

Vl2 CCC deform. 545 B 545 M 548 M,p

Vl3 CCN bend. 226 B 226 M 226 M,p

// a V\4 CH3 deg. stretch. 3001 C 3001 VS 2999 S OV(i/,)

Vl5 CH2 anti, stretch. 2849 C 2849 S 2850 M

V-16 CH3 deg. deform. 1465 C 1465 S 1466 VS,dp

Vl7 CH2 twist. 1256 B 1256 VW 1270 VW,dp

Vis CH3 rock. 1022 E CF

Vis CH2 rock. 786 B 786 M 784 VW,dp

V20 CCN bend. 378 B 378 M 378 M,dp

V2 1 CH3 torsion 274 C 274 W

References

[1] IR.R. N. E. Duncan and G. J. Janz, J. Chem. Phys. 23, 434 (1955).

[2] IR.R.Th. T. Fujiyama and T. Shimanouchi, unpublished.

48
No. 53

Molecule: Propane CH3CH2CH3

Symmetry C2v Symmetry number = 2

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ l cm

- ' (Matrix (Liquid)

isolation)

«1 Vi CH:j deg. stretch. 2962 C 2962 S SF(^15,^22)-

1'2 CH:j sym. stretch. 2876 C 2876 S OV(r3), SF(^ih).

V:\ CH2 sym. stretch. 2876 C 2876 S OVM.

Va CH;[ deg. deform. 1470 C 1470 S SFft'w, ^4 ). v5 CH2 scissors 1449 C 1449 W

(solid) vH CH;) sym. deform. 1388 B 1388 M

V! CH.) rock. 1154 B 1154 M 1152 W

v» CC stretch. 870 B 870 S 867 S

CCC deform. 371 B 370.6 375 W

(gas) a> VlU CH;, deg. stretch. 2967 C ia 2967 M

I'll CH;t deg. deform. 1451 C ia 1451 S

V\2 CH2 twist. 1278 C ia 1278 W

t'l.s CH:i rock. 940 D ia 940 VW

V\A CH:i torsion 200 E ia CF [7J. b> V i:> CH.t deg. stretch. 2962 C 2962 S SF(r>i,^22).

^IK CH;t sym. stretch. 2876 C 2876 S SF(ja>).

V\7 CH.t deg. deform. 1470 C 1470 S SF(r>4, p24 ). VlH CH:i sym. deform. 1375 B 1375 S

V ill CH2 wag. 1336 B 1336 M 1338 M

V>n CC stretch. 1051 B 1051 M 1054 M

Vll CH3 rock. 918 B 918 M

b. V22 CH.t deg. stretch. 2962 C 2962 S SF(i/,,i/, 5 ).

V2-A CH2 anti, stretch. 2910 C 2910 S

V2A CH:t deg. deform. 1470 C 1470 S SF( ^4 ,^17 ).

V>:, CH:i rock. 1186 B 1186 M

V2* CH2 rock. 741 B 741 S

U27 CH:i torsion 220 CF [7J.

References

[1] IR. D. M. Gates, J. Chem. Phys. 17, 393 (1949).

[2] IR. H. L. McMurry, V. Thornton, and F. E. Condon, J. Chem. Phys. 17, 918 (1949).

[3] IR. H. L. McMurry and V. Thornton, J. Chem. Phys. 19, 1014(1951).

[4] IR. J. J. Comeford and J. H. Gould, J. Mol. Spectr. 5, 474 (1960).

[5] Th. H. Takahashi, Nippon Kagaku Zasshi 82, 1304 (1961).

[6J IR. R. G. Snyder and J. H. Schachtschneider, Spectrochim. Acta 19, 85 (1963).

[7] Th. J. H. Schachtschneider and R. G. Snyder, Spectrochim. Acta 19, 117 (1963).

49
No. 54

Molecule: n-Butane CH3CH2CH2CH3 (trans form)

Symmetry C2 h Symmetry number = 2

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ ] cm~ ] (Matrix (Solid)

isolation)

a,j V\ CH3 deg. stretch. 2965 C ia 2965 (9) SF(v2»).

v-l CH3 sym. stretch. 2872 C ia 2872 (8)

v-.i CH2 sym. stretch. 2853 D ia 2853 ( 8 ) V4 CH.} deg. deform. 1460 C ia 1460 (2) SF(ia22 ). Va CH2 scissors 1442 D ia 1442 (3) V* CH.( sym. deform. 1382 C ia CF[9],

V7 CH2 wag. 1361 D ia CF[9],

v« CH3 rock. 1151 C ia 1151(4)

CC stretch. 1059 C ia 1059 (5)

I'll) CC stretch. 837 C ia 837 ( 6)

I'll CCC deform. 425 C ia 425 (4)

CLu ^12 CH3 deg. stretch. 2968 C 2968 S ia SF(p27 ). Via CH2 anti, stretch. 2930 C 2930 S ia V 1 4 CH3 deg. deform. 1461 B 1461 S ia SF(r’3„). V\a CH2 twist. 1257 C 1257 W ia (solid)

Vui CH3 rock. 948 B 948 M ia v 1

7

CH2 rock., 731 B 731 S ia VlH CH,j-CH2 torsion 194 E ia CF[9J.

Vu, CH»-CH2 torsion. 102 E ia CF[9],

b„ vw CH3 deg. stretch. 2965 C ia 2965 (9) SF(^i).

v-n CH2 anti, stretch. 2912 C ia 2912(4)

V22 CH3 deg. deform. 1460 C ia 1460 (2) SF^).

v2:, CH2 twist. 1300 C ia 1300 (4) V>4 CH3 rock. 1180 D ia CF[9],

v-ia CH2 rock. 803 D ia CF[9],

V'Hy CH3-CH2 torsion. 225 E ia CF[9],

bu v-n CH3 deg. stretch. 2968 C 2968 S ia SFUq 2 ).

V-1H CH3 sym. stretch. 2870 C 2870 S ia OV(r2!) ). Vn, CH2 sym. stretch. 2870 C 2870 S ia OV(r2S ).

V-M) CH3 deg. deform. 1461 B 1461 S ia SF(i/ u), OV^n).

v-.u CH2 scissors. 1461 C 1461 S ia OV(t'3n).

v-.n CH3 sym. deform. 1379 B 1379 M ia

V-.VA CH2 wag. 1290 B 1290 W ia

V-.14 CC stretch. 1009 C 1009 W ia (solid) V35 CH3 rock. 964 B 964 M ia V-M CCC deform. 271 E ia CF[9J.

References

[lj R. N. Sheppard and G. J. Szasz, J. Cliem. Phys. 17, 86 (1949).

|2] IR. D. W. E. Axford and D. H. Rank, J. Chem. Phys. 17, 430 (1949).

[3| R. T. Shimanouchi and S. Mizushima. J,. Chem. Phys. 17, 1102 (1949).

[4] R. S. Mizushima and T. Shimanouchi, J. Am. Chem. Soc. 71, 1320 (1949).

[5] IR.R. J. K. Brown, N. Sheppard, and D. M. Simpson, Phil. Trans. Roy. Soc. (London) 247A,

35 (1954).

[6| Th. R. I. Podlovchenko and M. M. Sushchinskii. Optika i spektroskopiya 2, 49 (1957).

[7] IR. J. J. Comeford and J. H. Gould, J. Mol. Spectroscopy 5, 474 (1960).

[8] IR. R. G. Snyder and J. H. Schachtschneider, Spectrochim. Acta 19, 85 (1963).

|9] Th. J. H. Schachtschneider and R. G. Snyder, Spectrochim. Acta 19, 117 (1963).

50
Molecule: n-Butane CH3CH2CH2CH3

(gauche form)

No. 55

Symmetry C2 Symmetry number =2

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~ ] cm

~ 1 (Liquid) (Liquid) a P CH.t deg. stretch. a 2968 C

P> CH3 deg. stretch. a 2968 C

Pi CH2 anti, stretch. a 2920 D

Pi CH3 sym. stretch. a 2870 C

P-, CH2 sym. stretch. a 2860 D

Pi CH3 deg. deform. a 1460 C

P CH.t deg. deform. a 1460 C

P< CH2 scissors a 1450 D

Pi CH3 sym. deform. a 1380 C

Pin CH> wag. 1350 C 1350 W

Pi CH2 twist. 1281 C 1281 (0) P2 CH3 rock. 1168 D 1168 (0) Pli CC stretch. 1077 D 1077(1) P

CH3 rock. 980 D 980 (2) OV(p32 ). P.> CC stretch. 827 D 827 (6) P« CH2 rock. 788 C 788 M 789 (2) P 7 CCC deform. 320 C 320(1)

Pk CH3-CH2 torsion 201 E CF[5J.

Pii CH2 -CH2 torsion 101 E CF[5],

b Po CH3 deg. stretch. a 2968 C

P>1 CH3 deg. stretch. a 2968 C

P-2 CH2 anti, stretch. a 2920 D

P-3 CH3 sym. stretch. a 2870 C

Via CH-2 sym. stretch. a 2860 D

V>:, C

3 deg. deform. a 1460 C

P-« CH3 deg. deform. a 1460 C

Pi 7 CH2 scissors a 1450 D

Pk CH3 sym. deform. a 1380 C

CH2 wag. 1370 D 1370 VW

PiO CH2 twist. 1233 C 1233 W

Pil CC stretch. 1133 D 1133 M

Pi2 CH3 rock. 980 D 980 (2) OV(p4 ).

Pi:i CH3 rock. 955 C 955 (lb)

Pi4 CH-2 rock. 747 C 747 S

Pi5 CCC deform. 469 D CF[5J.

Pi« CH3-CH2 torsion 197 E CF[5J.

a Deduced from the corresponding frequencies of the trans form.

References

[1] R. N. Sheppard and G. J. Szasz, J. Chem. Phys. 17, 86 (1949).

[2] IR. D. W. E. Axford and D. H. Rank, J. Chem. Phys. 17, 430 (1949).

[3] R. S. Mizushima and T. Shimanouchi, J. Am. Chem. Soc. 71, 1320 (1949).

[4] Th. R. I. Podlovchenko and M. M. Sushchinskii, Optika i spektroskopiya 2, 49 (1957).

[5] Th. R. G. Snyder and J. H. Schachtschneider, Spectrochim. Acta 21, 169(1965).

51
Molecule: Benzene CeH6 No. 56

Symmetry D6h Symmetry number = 12

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

Infrared Raman Comments

cm~' cm~'

(Liquid)

a \ f/ Vi CH stretch. 3062 C ia 3061.9 VS, p

V-z Ring stretch. 992 C ia 991.6 VS, p

(breathing)

d'lff V-.i CH bend. 1326 E ia 1326 VW

a>„ Va CH bend. 673 B 673 S ia bm Vr, CH stretch. 3068 C 3067.57 VW ia (solid)

Vh Ring deform. 1010 C 1010 W ia (solid)

b>,i V- CH bend. 995 E ia ia OC[2],

Vh Ring deform. 703 E ia ia OC[l,2J.

b>„ Vn Ring stretch. 1310 C 1310 W ia (Kekule) (liquid) VU) CH bend. 1150 C 1150 W ia (liquid)

eta Vii CH bend. 849 C ia 848.9 M, dp

e\„ Viz CH stretch. 3063 E

1 3080 S

[3030 S

ia FR(ri:i + %).

(liquid)

Viz Ring stretch. 1486 B 1486 S ia + deform. (gas)

Via CH bend. 1038 B 1038 S ia (gas)

e-in Viz CH stretch. 3047 C ia 3046.8 S, dp

11606.4 S, dp

V\ H Ring stretch. 1596 E ia 11584.6 S, dp ER(r2 + p ih ).

Vi 7 CH bend. 1178 C ia 1178.0 S, dp

ViH Ring deform. 606 C ia 605.6 S, dp

e-zu Via CH bend. 975 C 975 W ia (liquid)

V-ZQ Ring deform. 410 C

1 417.7

1 403.0

ia

(solid)

References

[1] IR.R. N. Herzfeld, C. K. Ingold and H. G. Poole. J. Chem. Soc. 316 (1946).

[2] IR. R. D. Mair and D. F. Hornig, J. Chem. Phys. 17, 1236 (1949).

[3] IR. H. Spedding and D. H. Whiffen, Proc. Roy. Soc. (London) A2 3 8, 245 (1956).

[4] Th. S. Califano and B. Crawford. Jr., Speetroehim. Acta 16, 889 (1960).

[5] Th. J. R. Scherer and J. Overend, Speetroehim. Acta 17, 719 (1961).

[6] IR. J. L. Hollenberg and D. A. Dows, J. Chem. Phys. 37, 1300 (1962).

52
Molecule: Benzene-<i(; C«D«

No. 57

Symmetry D6h Symmetry number = 12

Selected

Sym.

class

No.

Approximate

type of mode

value of

fre- quency

Infrared Raman Comments

cm -1 cm 1 (Liquid) a i</ V\ CD stretch. 2293 C ia 2292.6 VS, p

V-2 Ring stretch. 943 C ia 943.2 VS, p

(breathing)

CL 2<i V-.f CD bend. 1037 E ia ia oqij.

CL'lu Va CD bend. 497 C 496.5 S ia (liquid)

b\n Vt, CD stretch. 2292 E 2292 VW ia OC[lJ.

(solid)

1 970.48

Ring deform. 969 C 969.77

[ 966.76

ia

(solid)

biti Vi CD bend. 827 E ia ia OC[l J. Vh Ring deform. 601 E ia ia OC[lJ.

1 1287.51

b-2u VH Ring stretch. 1286 C 1286.41 ia (Kekule) [ 1285.14

(solid)

Cio CD bend. 824 C

f 825.2

{ 822.57

ia

(solid) e Ul Vu CD bend. 662 C ia 661.7 M, dp

Ci a Vvi CD stretch. 2287 C 2287 S ia (gas)

Vi 3 Ring stretch. 1335 B 1335 M ia + deform. (gas)

CD bend. 814 B 814 S ia (gas)

e-m V\:, CD stretch. 2265 C ia 2264.9 S, dp

t^n; Ring stretch. 1552 C ia 1551.5 S, dp

^17 CD bend. 867 C ia 867.3 S, dp

ClH Ring deform. 577 C ia 577.4 M, dp

’ 799.91

797.37

e-2 u V\f) CD bend. 795 C 794.64

790.9

ia

1 790.3

i (solid)

V-U) Ring deform. 352 E ia ia oqij.

References

[1] IR.R. N. Herzfeld, C. K. Ingold and H. G. Poole, J. Chem. Soc. 316 (1946).

[2] Th. S. Califano and B. Crawford, Jr., Spectrochim. Acta 16, 889 (1960).

[3] Th. J. R. Scherer and J. Overend, Spectrochim. Acta 17, 719 (1961).

[4] IR. D. A. Dows and A. L. Pratt, Spectrochim. Acta 18, 433 (1962).

[5] IR. J. L. Hollenberg andD. A. Dows, J. Chem. Phys. 37, 1300 (1962).

53
No. 58

Molecule: Cyclohexane C3H12

Symmetry D3h Symmetry number = 6

Selected

Sym.

class

No.

Approximate

type of mode

value of

fre- quency

Infrared Raman Comments

cm _1 cm~ 1 (Liquid)

Cllg P\ CH2 anti, stretch. 2930 E ia (2938 VS,p

[2923 VS,p

FR(21/3).

v2 CH2 sym. stretch. 2852 C ia 2852 VS,p

P3 CH2 scissors 1465 C ia 1465 M,p

P4 CH2 rock. 1157 C ia 1157 S,p

Vh CC stretch. 802 C ia 802 VS,p

V6 CCC deform. 383 C ia 383 M,p

+ CC torsion

d\u V7 CH2 twist, (vs) 1383 C ia, 1383* ia CF[3,5],

p» CH2 wag. (p7) 1157 C ia, 1157* ia CF[3,5], P9 CC stretch. 1057 C ia, 1057* ia CF[3,5].

+ CC torsion a2g V\o CH2 wag. 1437 C ia, 1437* ia CF[3,5].

P}1 CH2 twist. 1090 C ia, 1090* ia CF[3,5]. a2u V\ 2 CH2 anti, stretch. 2915 E 2915 M ia P\3 CH2 sym. stretch. 2860 E ia SF(v2 ,pis,v26). P\\ CH2 scissors 1437 C 1437 M ia

P15 CH2 rock. (^16) 1030 D

(1040 M

[1016

M

ia FR(i^23 + P32).

*^16 CCC deform. (z^i 5 ) 523 A 523 W ia

eg P\ 7 CH2 anti, stretch. 2930 E ia SF(i'i,j'i 2, ^5 ). PlS CH2 sym. stretch. 2897 E ia 2897 M,vb

P 19 CH2 scissors 1443 C ia 1443 S,dp

P20 CH2 wag. 1347 C ia 1347 S,dp

P21 CH2 twist. 1266 C ia 1266 VS,dp

P22 CC stretch. 1027 C ia 1027 VS,dp

P23 CH2 rock. 785 C ia, 785* 785 VW,dp

P24 CCC deform. 426 C ia 426 S,dp

+ CC torsion eu P25 CH2 anti, stretch. 2933 A 2933 VS ia

P26 CH2 sym. stretch. 2863 A 2863 VS ia

P27 CH2 scissors 1457 A 1457 VS ia

P2H CH2 wag. 1355 B 1355 W ia

P23 CH2 twist. 1261 A 1261 S ia P30 CH2 rock. 907 B 907 S ia P31 CC stretch. 863 A 863 S ia P32 CCC deform. 248 C 248 VW ia + CC torsion (liquid)

Note 1. Reference 3 gives the frequencies calculated from the modified UreyBradley force constants for hydrocarbons. Reference 5 gives those from the general

internal force constants for hydrocarbons. These two sets of calculated frequencies

are in agreement with each other within the deviation of 65 cm*1 for the A tu and A2g vibrations.

Note 2. Reference 4 gives different assignments for the CH2 rocking and skeletal deformation vibrations.

Note 3. The frequencies with asterisk are observed in the crystalline state at about

90 °K (ref. 9). Note 4. An alternative assignment for 1^5 is 910 cm*1 (see refs. 9 and 3).

54
References

[1] R.

[2] R.

[3] IR.Th.

1 4] IR.R.

[5] Th.

[6] Th.

[7] Th.

[8] IR.

[9] IR.

A. Langseth and B. Bak, J. Chem. Phys. 8, 403 (1940). N. I. Peokof’eva, L. M. Sverdlov and M. M. Sushchinskii, Optics and Spectros.

15 , 250 (1963). H. Takah ashi, T. Shimanouchi, K. Fukushima, and T. Miyazawa, J. Mol. Spectroscopy 13 , 43 (1964).

F. A. Miller and H. R. Colob, Spectrochim. Acta 20, 1517 (1964). R. G. Snyder and J. H. Schachtschneider, Spectrochim. Acta 21, 169 (1965). H. Takahashi and T. Shimanouchi, to he published.

C. W. Beckett, K. S. Pitzer, and R. Spitzer, J. Am. Chem. Soc. 69, 2488 (1947).

S. Abramowitz and R. P. Bauman, J. Chem. Phys. 39, 2757 (1963) and thesis S. Abramowitz.

D. A. Dows, J. Mol. Spectroscopy 16, 302 (1965).

55
Molecule: Cyclohexane-di2

No. 59

CeDi2

Symmetry D3h Symmetry number = 6

Sym.

class

No.

Approximate

type of mode

Selected

value of

fre- quency

1 nfrared Raman Comments

cm 1 cm~'

(Cas) (Liquid) a m to CD, anti, stretch. 2152 C ia 2152 VS, p

e. CD, sym. stretch. 2082 C ia 2082 VS, p

V:\ CD, scissors 1117 C ia 1117 M,

p

Va CD, rock. 1012 C ia 1012 W.p

f.-> CC stretch. 723 C ia 723 VS, p

f|i CCC deform. 298 C ia 298 W,p

+ CC torsion a w, v- CD, twist, (eH ) 864 E ia ia CF|4|.

CD, wag. (f7 ) 842 E ia ia CF[4|.

f«l CC stretch. + CC 1187 E ia ia CF|4|.

torsion

a>,i f10 CD, wag. 1126 E ia ia CE|4|.

fll CD, twist. 778 E ia ia CE|4|. a2u Vvi CD, anti, stretch. 2206 C 2206 VS ia ON <f,-,). v I. t CD, sym. stretch. • 2108 C 2108 VS ia ( ) \ ( e,(i ). f|4 CD, scissors 1091 B 1091 VS ia

fir. CD, rock. (f l(i ) 917 A 917 VS ia fm CCC deform. (f|.-,) 395 B 395 S ia f|7 CD, anti, stretch. 2199 C ia 2199 VS. dp

f|K CD, sym. stretch. 21(14 C ia 2104 \ S, dp

fin CD, scissors 1071 C ia 1071 M, dp

v>» CD, wag. 1212 C ia 1212 M, dp

v>\ CD, twist. 937 C ia 937 S. dp

v-ll CC stretch. 795 C ia 795 S. dp

faa CD, rock. 637 C ia 637 \V, dp

fji CCC deform. + CC 373 C. ia 373 M, dp

torsion

e„ 17,.-, CD, anti, stretch. 2206 C 2206 VS ia OV(f,,). V-M CD, sym. stretch. 2108 C 2108 VS ia OV(f|;i ). Vn CD, scissors 1069 C 1069 \I ia (liquid)

V-1H CD, wag. 1 165 A 1 165 \ S ia CD, twist. 991 A 991 VS ia

f;in CD, rock. 687 B 687 S ia

V:n C(^ stretch. 720 A 720 S ia

fill' CCC deform. + CC 203 C ia CF

torsion

Note I. As for the calculated frequencies, see C(i H|,.

References

[ 1 ] IR.

[2] R.

[3] IR.R.

[4] IR.R.Th.

S. Abramowitz and R. P. Bauman, J. Chem. Phys. 39, 2757 (1963) and thesis

S. Abramowitz.

N. I. Peokof’eva, L. M. Sverdlov, and M. M. Sushehinskii, Optics and Spectros.

15, 250 (1963). F. A. Miller and H. R. Golob, Spectrochim Acta 20, 1517 (1964). H. Takahashi and T. Shimanouchi, to be published.

5,6

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