U.S. DEPARTMENT OF COMMERCE / National Bureau of Standards

NSRDS

Electronic Absorption

and Internal and External

Vibrational Data of

Atomic and Molecular Ions

Doped in Alkali Halide

Crystals

I QC

10o

\.U573

rto* 5Z

L. c.t J
NATIONAL BUREAU OF STANDARDS

The National Bureau of Standards 1 was established by an act of Congress March 3, 1901. The Bureau’s overall goal is to strengthen and advance the Nation’s science and technology

and facilitate their effective application for public benefit. To this end, the Bureau conducts

research and provides: (1) a basis for the Nation’s physical measurement system, (2) scientific and technological services for industry and government. (3) a technical basis for equity in trade,

and (4) technical services to promote public safety. The Bureau consists of the Institute for Basic Standards, the Institute for Materials Research, the Institute for Applied Technology,

the Institute for Computer Sciences and Technology, and the Office for Information Programs.

THE INSTITUTE FOR BASIC STANDARDS provides the central basis within the United

States of a complete and consistent system of physical measurement; coordinates that system

with measurement systems of other nations; and furnishes essential services leading to accurate and uniform physical measurements throughout the Nation’s scientific community, industry,

and commerce. The Institute consists of a Center for Radiation Research, an Office of Measurement Services and the following divisions: Applied Mathematics — Electricity — Mechanics — Heat — Optical Physics — Nuclear

Sciences 2 — Applied Radiation 2 — Quantum Electronics 3 — Electromagnetics 3 — Time

and Frequency 3 — Laboratory Astrophysics 3 — Cryogenics 3

. THE INSTITUTE FOR MATERIALS RESEARCH conducts materials research leading to improved methods of measurement, standards, and data on the properties of well-characterized

materials needed by industry, commerce, educational institutions, and Government; provides

advisory and research services to other Government agencies; and develops, produces, and

distributes standard reference materials. The Institute consists of the Office of Standard

Reference Materials and the following divisions: Analytical Chemistry — Polymers — Metallurgy — Inorganic Materials — Reactor

Radiation — Physical Chemistry.

THE INSTITUTE FOR APPLIED TECHNOLOGY provides technical services to promote

the use of available technology and to facilitate technological innovation in industry and

Government; cooperates with public and private organizations leading to the development of

technological standards (including mandatory safety standards), codes and methods of test; and provides technical advice and services to Government agencies upon request. The Institute consists of a Center for Building Technology and the following divisions and offices: Engineering and Product Standards — Weights and Measures — Invention and Innovation — Product Evaluation Technology — Electronic Technology — Technical Analysis — Measurement Engineering — Structures, Materials, and Life Safety 4 — Building

Environment 4 — Technical Evaluation and Application 4 — Fire Technology.

THE INSTITUTE FOR COMPUTER SCIENCES AND TECHNOLOGY conducts research and provides technical services designed to aid Government agencies in improving cost effec- tiveness in the conduct of their programs through the selection, acquisition, and effective

utilization of automatic data processing equipment; and serves as the principal focus within

the executive branch for the development of Federal standards for automatic data processing

equipment, techniques, and computer languages. The Institute consists of the following

divisions; Computer Services — Systems and Software — Computer Systems Engineering — Information Technology.

THE OFFICE FOR INFORMATION PROGRAMS promotes optimum dissemination and

accessibility of scientific information generated within NBS and other agencies of the Federal

Government; promotes the development of the National Standard Reference Data System and

a system of information analysis centers dealing with the broader aspects of the National

Measurement System; provides appropriate services to ensure that the NBS staff has optimum

accessibility to the scientific information of the world. The Office consists of the following

organizational units: Office of Standard Reference Data — Office of Information Activities — Office of Technical

Publications — Library — Office of International Relations.

1 Headquarters and Laboratories at Gaithersburg, Maryland, unless otherwise noted; mailing address Washington, D.C. 20234.

2 Part of the Center for Radiation Research.

2 Located at Boulder, Colorado 80302.

* Part of the Center for Building Technology.
SJG 1 ^ ^74

Electronic Absorption and

£100 B 5j3 Internal and External Vibrational Data of Atomic

m and Molecular Ions Doped in Alkali Halide Crystals

*

S. C. Jain, A. V. R. Warrier,

and S. K. Agarwal

Department of Physics

Indian Institute of Technology

New Delhi 110029, India

* NSRDS - N8S 52

U.S. DEPARTMENT OF COMMERCE, Frederick B. Dent, Secretary

J.Si NATIONAL BUREAU OF STANDARDS, Richard W. Roberts, Director

Issued July 1974
Library of Congress Catalog Number: 74-600010

NSRDS-NBS 52

Nat. Stand. Ref. Data Ser., Nat. Bur. Stand. (U.S.), 52, 59 pages (July 1974)

CODEN: NSRDAP

1974 by the Secretary of Commerce on Behalf of the United States Government

U.S. GOVERNMENT PRINTING OFFICE

WASHINGTON: 1974

For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. (Order by SD Catalog No. 03.48:52). Price 95 cents. Stock Number 0303-01262

20402
Foreword

The National Standard Reference Data System provides access to the quantitative data of physical science, critically evaluated and compiled for convenience and readily accessible through a variety of distribution channels. The System was established in 1963 by action of the President’s

Office of Science and Technology and the Federal Council for Science and Technology, and

responsibility to administer it was assigned to the National Bureau of Standards.

NSRDS receives advice and planning assistance from a Review Committee of the National

Research Council of the National Academy of Sciences-National Academy of Engineering. A number of Advisory Panels, each concerned with a single technical area, meet regularly to examine

major portions of the program, assign relative priorities, and identify specific key problems in need of further attention. For selected specific topics, the Advisory Panels sponsor subpanels

which make detailed studies of users’ needs, the present state of knowledge, and existing data re- sources as a basis for recommending one or more data compilation activities. This assembly of advisory services contributes greatly to the guidance of NSRDS activities. The System now includes a complex of data centers and other activities in academic insti- tutions and other laboratories. Components of the NSRDS produce compilations of critically

evaluated data, reviews of the state of quantitative knowledge in specialized areas, and computations of useful functions derived from standard reference data. The centers and projects also establish criteria for evaluation and compilation of data and recommend improvements in ex- perimental techniques. They are normally associated with research in the relevant field. The technical scope of NSRDS is indicated by the categories of projects active or being

planned : nuclear properties, atomic and molecular properties, solid state properties, thermodynamic and transport properties, chemical kinetics, and colloid and surface properties.

Reliable data on the properties of matter and materials is a major foundation of scientific and technical progress. Such important activities as basic scientific research, industrial quality control, development of new materials for building and other technologies, measuring and correcting

environmental pollution depend on quality reference data. In NSRDS, the Bureau’s responsibility

to support American science, industry, and commerce is vitally fulfilled.

Richard W. Roberts, Director

m

Contents

Page Foreword iii Introduction 1 References 2

PART I. ELECTRONIC ABSORPTION OF IMPURITY CENTERS DOPED

IN ALKALI HALIDE CRYSTALS

1. Cu, Ag and Au Centers. Tables 1-3 5-7

2. Mg, Ca, Sr and Ba Centers. Tables 4-7 7-8

3. Zn, Cd and Hg Centers. Tables 8-10 8-9

4. Ga, In, Tl, Pb, Sn, Ge and Bi Centers. Tables 11-17 10-14

5. Ti, V, Cr, Mn, Co and Ni Centers. Tables 18-23 14-18

6. Rh and Pd Centers. Tables 24, 25 18

7. Eu, Sm, Yb and Ho Centers. Tables 26-29 19-21

8. Uranium Centers. Table 30 21

9. H and D Centers. Table 31 21

10. Halogen Centers. Table 32 22

11. O, S, Se Centers. Tables 33-35 22

12. OH and OD Centers. Table 36 23

13. Complex Ion Centers. Tables 37—43 23-25

PART II. VIBRATIONAL FREQUENCIES OF INTERNAL MODES OF

COMPLEX IONS DOPED IN ALKALI HALIDE CRYSTALS

1. Point Group Symmetry of Molecular Ions. Table 44 29

2. Homonuclear Diatomic Molecular Ions. Table 45 30

3. Heteronuclear Diatomic Molecular Ions. Table 46 31

4. Triatomic Symmetric Linear Ions. Table 47 32

5. Triatomic Asymmetric Linear Ions. Table 48 33

6. Triatomic Bent Ions. Table 49 34

7. Tetraatomic Pyramidal Ions. Table 50 35

8. Tetraatomic Planar Ions. Table 51 36

9. Pentaatomic Tetrahedral Ions. Table 52 37

10. Polyatomic Ions. Table 53 43

PART III. EXTERNAL VIBRATIONAL FREQUENCIES OF IMPURITY

CENTERS DOPED IN ALKALI HALIDE CRYSTALS

1. Point Impurities. Table 54 47

2. Complexions. Table 55 50
'
Electronic Absorption and Internal and External Vibrational

Data of Atomic and Molecular Ions Doped in Alkali Halide

Crystals

S. C. Jain,* A. V. R. Warrier,** and S. K. Agarwal**

Department of Physics

Indian Institute of Technology

New Delhi 110029, India

Spectral data for more than 70 atomic and molecular ions doped in alkali halide crystals are

tabulated. The tables include electronic absorption data, listings of internal vibrational frequencies

of doped complex ions, and tabulations of the frequencies of external modes. The data that appear

in the tables were selected on the basis of the consistency among different authors, the types of in- struments, and the temperature of measurement. In addition to the data, the tables include the spectroscopic assignments given by the authors in the references cited. Key words: Atomic ions; doped alkali halide crystals; external vibrational modes; internal vibrational modes; molecular ions. Introduction

When atomic and molecular impurity ions are doped in crystals, the optical (electronic) absorption

spectrum of the ions will be modified. Because of

the low symmetry of the environment (lower than

spherical symmetry), the degeneracies of free ion

levels can split and transitions between these split

levels can take place. These transitions give rise

to the so-called crystal field bands and can be in- terpreted on the basis of crystal field theory [l]. 1 In

addition, transitions involving the transfer of charge

between the impurity ion and the surrounding

ligands also can occur, giving rise to strong charge

transfer absorption bands. If there is considerable

overlap of the wave functions of the impurity ion

and the ligands, further modifications of the

spectra occur due to covalency effects, and the

observed spectra can only be explained on the basis

of ligand field theory and molecular orbital theory

[2, 3]. Thus the study of optical absorption spectra

gives information about the symmetry of the crystal

field as well as the nature of the interaction between

the impurity ion and the host lattice. The crystal

field transitions are parity forbidden and they are phonon assisted. Temperature dependence of the

optical spectrum gives the nature of the transitions.

Complex molecular ions, in addition to their

electronic spectrum, give infrared and Raman

spectra due to their internal vibrational modes

[4, 5], When such ions are doped in crystals, their

*Also at the Solid State Physics Laboratory, Lucknow Road, Delhi 110007, India. **Present address: Solid State Physics Laboratory, Lucknow Road, Delhi 110007,

India.

1 Figures in brackets indicate literature references on page 2.

vibrational frequencies shift depending upon the

size of the host lattice sites and of the complex

ion as well as the interaction between the ions [6]. Splitting of the degenerate vibrational modes may

occur due to lowering of the symmetry of the ion

whenever defects are present in the nearest or next nearest neighbour positions [7, 8]. These

internal vibrational modes can sometimes show

side bands due to combination with the external

modes of impurity host lattice system [9, 10].

Therefore, a detailed study of the internal vibrational modes of molecular impurities gives useful

information about the defect properties as well

as the phonon spectrum of the host lattice. When impurity ions are introduced into a lattice,

new modes are induced in the lattice giving rise

to an absorption spectrum in the far infrared. If the impurity is monoatomic, only localized, resonant,

or gap modes are induced, depending upon whether

the new absorption appears above the optical band,

in the acoustic continuum, or in the gap between the

acoustic and optical branches, respectively [11].

Whether the impurity will induce a localized,

resonant, or gap mode will depend upon the relative mass of the impurity ion with respect to the ion it replaces, as well as the force constant between the

impurity and the host lattice ions. If, on the other

hand, the impurity is molecular, in addition to these

modes, librational as well as tunneling modes are

also induced [7, 12]. These new modes can give rise

to far infrared absorption and Raman scattering,

and show strong resonant scattering of phonons in

thermal conductivity. Impurity also breaks down the

1
translational symmetry of the lattice, and vibrations

at all points in the Brillouin zone become infrared

and/or Raman active depending upon the symmetry

of the mode. Thus impurity induced infrared and

Raman spectra can be used to map the phonon

spectrum of the host lattice. Alkali halide crystals doped with more than 70

different impurity ions have been investigated from

the above-mentioned points of view [13]. This is because of the ease with which pure and wellcharacterized alkali halide crystals can be grown,

as well as to their almost perfect ionic nature,

precise knowledge of the location of the ions and

the neighbouring defect in the lattice, etc. The

cubic symmetry of the crystal field and the exact

knowledge of the symmetry of the field due to defects in the vicinity of the impurity ion, make

alkali halides excellent hosts to study and to interpret the optical and other defect sensitive

properties of ions.

In alkali halide crystals most of the impurities

enter substitutionally at the cation or anion site depending upon whether the impurity is cationic

or anionic, respectively. In the case of a few large

complex impurity ions such as Co(CN)6, Fe(CN)6,

etc., the impurity replaces a complex group of seven

lattice sites MX6 (M-alkali ion and X-halide ion). If the impurity is aliovalent, extra charge is compensated by the creation of vacancies or by intentionally doped or background charge compensating

impurity ions. The symmetry of the environment

about the Co(CN)6 group is determined by the location of the charge compensating entity.

Impurity doped alkali halides find many modern

technological applications. Tl+ doped Nal is a well

known scintillator and is extensively used in y-ray

scintillation counters. Color centers in alkali halides

are being used successfully as memory devices.

Recently it has been shown that the paraelectric

property of LF in KC1 can be used as a thermometer

to measure extremely low temperatures.

With the wide academic interest and potential

technological applications of impurity centers in

alkali halides, the availability of comprehensive

optical data of different centers in alkali halide

crystals is extremely valuable. The amount of

literature on the optical properties of impurity

centers in alkali halides has grown so much in the

last ten years that it is extremely difficult for one

to keep track of the development. It is therefore

desirable to gather all the optical data in one place

for all the impurity centers doped in alkali halides

so that this can serve as a ready reference.

The following tables on the optical properties

have been prepared by critically going through more

than 500 papers listed in [13] and other relevant

papers published before 1964. The references are given for those papers from which the actual data

reported is taken. If more than one paper exists

on the same impurity ion, the data are evaluated on the basis of the experimental procedures used,

the resolution and accuracy of the instruments

employed for measurements, consistency of the

data between different authors, and quality of the

samples on which measurements were made.

Assignments given for the absorption bands in the

table are those reported in the references.

The reference data are divided into three parts.

In Part I the electronic absorption bands are tabulated. Here the peak positions are given in

nanometers (nm). The data given in eV in the paper

are converted to nm using the relation 1 eV = 1239.0 nm. Wherever possible the temperature of measure- ment is also indicated for each band.

Since the available data on halfwidth/oscillator

strength of the absorption bands are meager and not consistent among different authors, we have not

included them.

The data on the internal vibrational frequencies

of complex ions doped in alkali halide crystals are given in Part II.

2 Here the frequencies are given in

wavenumbers (cm-1

) and the ions are arranged in

the order of increasing number of atoms in the

complex ions.

In Part III the frequencies of the external modes

are presented. Here again the frequencies are in

wavenumbers (cm-1

). The data are presented first for monoatomic impurities and then for the molecular ions.

References are given at the end of each table.

References

[1] Ballhausen, C. J., Ligand Field Theory, McGraw Hill, N.Y.

(1962).

[2] Sugano, S., and Shulman, R. G., Phys. Rev. 130, 517 (1963).

[3] Ballhausen, C. J., and Gray, H. B., Molecular Orbital Theory,

Benjamin, N.Y. (1964).

[4] Herzberg, G., Infrared and Raman Spectra of Polyatomic

Molecules, Van Nostrand, N.Y. (1945).

[5] Nakamoto, K., Infrared Spectra of Inorganic and Coordination Compounds, John Wiley, N.Y. (1970).

[6] Field, G. R., and Sherman, W. F., J. Chem. Phys. 47, 2378

(1967).

[7] Decius, J. C., Coker, E. H., and Brenna, G. L., Spectrochim Acta 21 , 1281 (1963).

[8] Jain, S. C., Warrier, A. V. R., and Agarwal, S. K., Chem.

Phys. Letters 14, 211 (1972).

[9] Seward, W. D., and Narayanamurti, V., Phys. Rev. 148 , 463 (1963).

[10] Metselaar, R., and Van der Elsken, J., Phys. Rev. 165 , 359

(1968).

[11] Maradudin, A., Localized Excitations in Solids, Plenum

Press, N.Y. (1969) pp. 1-16.

[12] Wedding, B., and Klein, M. V., Phys. Rev. 177 , 1274 (1969).

[13] Jain, S. C., et al., Bibliographies on Properties of Defect Centers in Alkali Halides, Report No. NBS-OSRDB71-1, National Bureau of Standards, Washington, D.C.

(1971).

2 In keeping with commonly accepted conventions in molecular spectroscopy,

certain energies have been expressed in their wavenumber (cm-1

) equivalents. The

actual energy can be obtained by multiplying the cm-1 equivalent by he.

2
PART I.

Electronic Absorption of Impurity Centers Doped

in Alkali Halide Crystals

3

532-811 0 - 74 -2
’
Table 1. Optical absorption bands (in nm) of copper centers in alkali halides

Center NaCl KC1 KBr KI Assignment References

Cu2+ d 366 [ 1 ]

. d 300 —

[ 1 ]

• d 248 [ 1 ] b 243

'

; * — --- [2]

Cu+ c 372 [3]

__

c 305 [4]

e 282 b 284 c 292 278 [2,5]

c 257 c 261 c 263 262 [1,4, 5]

c 214 c 202 c 210 d 229 [1,4]

c 194 e 199 , [4, 6] c 185 c 186 i — — [6]

Cu° c 550 [7]

c 496 d 457 d 480 d 556 [1,7]

c 460 ' [7]

d 283 [ 1 ] Mr- —

d 246 d 247 d 251 [ 1 ] d 242 d 243 1 4^ [ 1 ] d 235 d 240 [ 1 ] d 233 d 236 [ 1 ] _

' c 232 c 233 __ [ 1 ] MM—

c 229 c 230 . 1 ^ [ 1 ] — c 225 — — [ 1 ]

Colloidal a 574 c 568 c 575 575 [ 1 , 8] Cu

413 — - — --- ' [8]

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

dTemperature between 4.2 and 77 K.References

[1] Kratzig, E., Timusk, T., and Martienssen, W., Phys. Stat.

Sol. 10, 709 (1965).

[2] Bohun, A., and Kaderka, M., Czech. J. Phys. B19, 1180

(1969).

[3] Ueta, M., Ikezawa, M., and Nagasaka, S., J. Phys. Soc. Japan 20, 1724 (1965).

[4] Fussgaenger, K., Phys. Stat. Sol. 34, 157 (1969).

[5] Dultz, W., and Sittig, R., Proc. Int. Sym. Color Centers in Alkali Halides, Rome (1968) pp. 86.

[6] Nagasaka, S., Ikezawa, M., and Ueta, M., J. Phys. Soc. Japan 20, 1540 (1965).

[7] Bohun, A., Slaky, P., Dolejsi, J., and Kaderka, M., Proc. Int. Sym. Color Centers in Alkali Halides, Rome (1968) pp. 41.

[8] Takeuchi, N., J. Phys. Soc. Japan 26 , 872 (1969).

Table 2. Optical absorption bands (in nm) of silver centers in alkali halides

Center NaCl NaBr KC1 KBr KI RbCl RbBr CsCl CsBr Csl Assignment References

Ag

2

+ COoo

a d 1137 [1 . 2] — b 630 [ 1 ] b 560 d 539 _ [ 1 . 2] b 460 [ 1 ] — =4 d 409 [2 ] — a 356 b 338 d 350 — — — — — [ 1 . 2 ] Ag+ d 225 a 242 a 244 a 241 d 276 Ag+ pairs [3.5]

d 230 [3.5] — a 229

’ [4]

5
Table 2. Optical absorption bands {in nm) of silver centers in alkali halides — Continued

Center NaCl NaBr KC1 KBr KI RbCl RbBr CsCl CsBr Csl Assignment References

a 222 [4]

d 214 d 225 d 238 d 253 d 223 d 243 [3.5]

d 210 d 219 d 233 [3.5]

d 225 [3. 5]

d 194 d 209 d 212 d 244 [3, 5]

d 218 d 222 [5]

d 212 d 218 [5]

d 188 d 200 [3]

d 191 d 198 d 208 [3.5]

b 163 — b 173 c 199 238 — — — — — — [5. 6. 7]

Ag° a 385 a 450 a 425 a 494 a 494 — — — — — Interstitial Ag atom.

[2. 4. 8]

c 420 c 445 c 470 c 410 [9] — — b 197 — [1]

Ag- b 435 (Ag-)z [10] — — b 403 (Ag“)2 [10]

b 330 — c 399 d 413.8 d 431 d 446.5 'Aig -*

3

Tlu (A) [11, 12, 13. 14] — — b 390 (Ag~)2 [10] — — b 330 (Ag-) 2 [10]

b 310 — d 381.5 d 396 d 415.8 — — — — d 432.8 'A,, 3T2u or 3EU (B)

[11. 12. 14]

b 275 c 285 d 296.5 d 311 d 301.5 d 308.5 d 328.8 ‘Ax, ‘Tlu (C) [10. 14]

b 283 (Ag-)2 [10] — — b 278 (Ag-)2 [10] — — b 267 (Ag“)2 [10] — — b 263 (Ag-)2 [10] — — b 228 (Ag-)2 [10]

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K.

References

[1] Delbecq, C. J., Hayes, W., O’Brien, M. C. M., and Yuster,

P. H., Proc. Roy. Soc. A271, 243 (1963).

[2] Kratzig, E., Timusk, T., and Martienssen, W., Phys. Stat.

Sol. 10 , 709 (1965).

[3] Fussgaenger, K., Martienssen, W., and Bilz, H., Phys.

Stat. Sol. 12, 383 (1965).

[4] Etzel, H. W., and Schulman, J. H., J. Chem. Phys. 22,

1549 (1954).

[5] Fussgaenger, K., Phys. Stat. Sol. 34, 157 (1969).

[6] Kojima, K., Sokurai, S., and Kojima, T., J. Phys. Soc. Japan 24 , 815 (1968).

[7] Onaka, R., Fukuda, A., Inohara, K., Mabuchi, T., and

Fujioka, Y., Japan J. Appl. Phys. 4, Suppl. 1, 631 (1965).

[8] Maenhent-van der Vorst, W., and Dekeyser, W., Physica 23,

903 (1957).

[9] Brown, F. C., Cavenett, B. C., and Hayes, W., Proc. Roy.

Soc. A300, 78 (1967).

[10] Yoshikawa, A., Tkezoe, H., Maruyama, I., and Onaka, R.,

J. Phys. Soc. Japan 32, 472 (1972).

[11] Topa, V., and Haragea, S., Phys. Stat. Sol. 16, 137 (1966).

[12] Kleemann, W., Z. Physik 215, 113 (1968).

[13] Kojima, K., Shimanuki, S., Maki, M., and Kojima, T., J. Phys. Soc. Japan 28, 1227 (1970).

[14] Kleemann, W., Z. Physik 214, 362 (1970).

6
Table 3. Optical absorption bands (in nm) of gold centers in alkali halides

Center NaCl KC1 KBr KI Assignment References

AuCLf a 320 J Ajg * X A2u [1] — a 226 — — X Alg *EU [1]

Au° — a 271 — — — [1]

Au- d 294 d 304 d 311 d 321.5 x Alg 3 Tlu (A) [2]

d 272.5 d 284 d 293.3 d 310.0 l Alg 3 T2u [2] or 3 EU (B)

d 220.7 d 228.3 d 235.6 d 245.5 x A19

X T1U (C) [2] d 195.6 d 202.5 d 209.2 d 219.0 (Di) [2]

b 172 d 175.5 — — (D2 ) ]3] Au a 555 [4] Colloids

aRoom temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

dTemperature between 4.2 and 77 K. References

[1] Takeuchi, N., Nishie, S., and Konishi, Y., Japan. J. Appl.

Phys. 8, 814 (1969).

[2] Fischer, F., Z. Physik 231, 293 (1970).

[3] Mabuchi T., Yoshikawa, A., and Onaka, R., J. Phys. Soc. Japan 28 , 805 (1970).

[4] Jain, S. C., and Sehgal, H. K., J. Phys. Chem. Sol. 33, 1161

(1972).

Table 4. Optical absorption bands (in nm) of Table 5. Optical absorption bands (in nm) of

magnesium ions in alkali halides calcium centers in alkali halides

Center LiF KC1 Assignment References Center NaCl KC1 KBr Assignment References

Mg2+ a 320 [1] Ca2+ b 469 b 596 b 697 L [1]

a 308 [2]

b 588 z, [2] b 216 a 272 — [1,2,3] b 398 er 00 CO b 554 Zs [1]

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

dTemperature between 4.2 and 77 K.

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K.

References

[1] Sootha, G. D., and Singh, D., Phys. Rev. 183, 842 (1969).

[2] Mort, J., Solid State Comm. 3, 263 (1965).

[3] Mort, J., Phys. Letters 21, 124 (1966).

References

[1] Kojima, K., J. Phys. Soc. Japan 19, 868 (1964).

[2] Yurachkovskii, P. A., and Gorbenko, P. K., Opt. and Spec.

20, 35 (1966).

7
Table 6. Optical absorption bands {in nm) of strontium centers in alkali halides

Center NaCl NaBr KC1 KBr KI RbCl Assignment References

Sr2+ b 834 z4 [1J

b 514 b 560 b 635 b 713 b 840 z2 [2, 3J

b 565 b 550 b 595. 617 h 658 b 664 Zi [2, 3, 4]

b 398 b 494 b 556 z:! [2, 3]

b 450 b 510 s [5] — — — b 198 — — — [5]

a Room temperature. 'Liquid helium temperature.

b Liquid air/nitrogen temperature. '‘Temperature between 4.2 and 77 K. References

[1J Ishiguro. M.. and Takeuchi, N., J. Phys. Soc. Japan 15, 1871 [3] Hingsammer, J., and Jodi, H., Phys. Letters 25A, 131

(1960). (1967).

[2] Kojima. K.. J. Phys. Soc. Japan 19, 868 (1964). [4] Gehrer, G., and Langer, H., Phys. Letters 26A, 232 (1968).

[5] Ohkura, H., Phys. Rev. 136, A446 (1964).

Table 7. Optical absorption bands (in nm) of

barium centers in alkali halides

Center KC1 KBr Assignment References

Ba2+ b 812 b 845 z2 [U

b 636 b 713 z2 [1]

b 599 — z, [2 J

a Room temperature. c Liquid helium temperature.

h Liquid air/nitrogen temperature. d Temperature between 4.2 and 77 K. References

[lj Kojima, K.. J. Phys. Soc. Japan 19, 868 (1964). [2j Jain. S. C., and Radhakrishna, S., J. Sci. and Ind. Res. 26,

324 (1967).

Table 8. Optical absorption bands (in nm) of

zinc centers in alkali halides

Center NaCl KC1 KBr KI

Assign- ment

Refer- ences

Zn2 + a 273 a 272 [L2J

a 256 a 212 a 245 [L 3J

a 189 a 200 a 202 — [4j

Zn 1 + — a 245 a 275 a 330 — [2, 3, 4]

Zn° — a 350 a 370 a 440 — [3,5]

a Room temperature. ' Liquid helium temperature.

b Liquid air/nitrogen temperature. ‘‘Temperature between 4.2 and 77 K. References

[lj Kuwabara. G., and Aoyagi, K., Japan. J. Appl. Phys. 4

Suppl. 1, 627 (1965).

[2j Ben-Dor, L., Glasner. A., and Zolotov, S., Phys. Stat. Sol. 18,593(1966).

[3J Ben-Dor, L., Glasner, A., and Zolotov, S., Solid State Chem.

4 , 4(1972).

[4] Jain, S. C., and Radhakrishna, S., Phys. Rev. 172, 972

(1968)-.

[5J Radhakrishna, S., Nuov. Cimento 48, 169 (1971).

8
Table 9. Optical absorption bands (in nm) of cadmium centers in alkali halides

Center NaCl NaBr KC1 KBr KI Assignment References

Cd2+ b 292 (Cd2+

) 2 [1]

a 278 a 280 b 275 — [1.2]

a 250 — [1]

a 263 (Cd2+

) 2 [1]

a 227 (Cd2+

) 2 [1]

a 212 b 235 — [1,2]

a 190 — a 190 a 202 — — [2.3]

Cd1 + a 310 a 300 a 310 a 340-3 10 a 355 [1,4,5]

a 300 (Cd+) 2 [1] — — — a 280 — — [1]

Cd° — — — a 365 a 510 — [2,5]

Cd Colloids a 270 a 275 a 275 a 300 a 310 ___ [2,4]

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K. References

[1] Ben-Dor, L., Glasner, A., and Zolotov, S., J. Solid State Chem. 4 , 4 (1972).

[2] Jain, S. C., and Radhakrishna, S., Phys. Rev. 172 , 972

(1968).

[3] Ben-Dor, L., Glasner, A., and Zolotov, S., Phvs. Stat. Sol. 18,593(1966).

[4] Jain, S. C., Sootha, G. D., and Jain, R. K., J. Phys. C. 1, 1220

(1968).

[5] Radhakrishna, S.. J. Phys. Soc. Japan 26, 1204 (1969).

Table 10. Optical absorption bands (in nm) of mercury centers in alkali halides

Center KC1 KBr KI Assignment References

Hg2 + a 265 (Hg2 +

) 2 [1]

a 245 b 300 a 347 [1.2]

,

J_»; b 275 a 290 __ [1] —-**. — a 275 +1- [1] Hg1 + a 410 a 455 [1]

b 315 ( Hg1 +

) 2 [1]

a 290 b 260 a 280 [1] — a 260 — [1J

Hg° a 345 —

a 425 [1J Hg2+ :OH- a 195 — — [2] HgO a 215 — — St [2]

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K. References

[1] Ben-Dor, L., Glasner. A., and Zolotov, S., J. Solid State [2] Allen, C. A., and Fredericks, W. J., Phys. Stat. Sol. 3a, 143 Chem. 2,549(1970). (1970). 9
Table 11 . Optical absorption bands (in nm) ofgallium centers in alkali halides.

Center NaCl KC1 KBr KI CsBr Csl Assignment References

Ga1 + c 307 (Ga1 +

) 2 [1] — — — b 287 b 288 b 310 ‘A^T.^A) [1,2,3]

b 272 b 261 b 272 ’A^T^A,) [L2]

b 265 b 255 b 265 — 1 Aly-^

3

Tlu( A2 ) [L2]

b 257 b 247 b 257 — b 269 b 290 1 Ai9—

3 EU or [1,2,3]

3 T2u (B)

c 241 c 228 c 245 c 275 (Ga1 +

) 2 [1]

b 216 — — — b 229 b 253 ’A^t^C) [4,5] — c 218 c 228 c 254 ‘A^Tj^Cx) [4] — c 214 c 225 c 251 — — ‘AurUTn.fC*) [4]

c 210 c 222 c 247 1 Alg-^

1

Ti u (C3 ) [4]

b 158 b 166 O’ CO CO — — — (D') [2]

Ga° — Ga° — — — — b 427 b 400 — [5] Ga°— Ga1 + — — — — — a 5 17-563 — [5]

a Room temperature.

h Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K. References

[lj Fukuda, A., J. Phys. Soc. Japan 26, 1006 (1969). [4] Fukuda, A., J. Phys. Soc. Japan 27, 96 (1969).

[2] Mabuchi, T., Fukuda, A., and Onaka, R., Science of Light [5] Osminin, V. S., and Zazubovich, S. G., Optics and Spec15, 79 (1966). troscopy 29, 491 (1970).

[3] Zazubovich, S. G., Phys. Stat. Sol. 38, 119 (1970).

Table 12. Optical absorption bands (in nm) of indium centers in alkali halides

Center NaCl KF KC1 KBr KI RbCl CsBr Assignment References

In l + c 330 < (In 1+

) 2 [1]

b 284 c 312 l Alg-* 3Tlu (A) [2,3]

b 302 a 284 b 290 c 297 a 325 c 284 * A i g

^

3 Tj u(A i

)

[3, 4, 5, 7]

b 295 a 265 b 282 c 293 a 309 c 281 1 A1!7-^ 3 T1u (A2 ) [3, 4, 5, 7]

b 276 a 246 b 265 c 280 a 291 — c 267 'Aig—

3 EU or

3 T2 u (B)

[3,4, 7]

c 248 c 266 c 292 (In 1+

) 2 [1]

c 238 a 213 b 228 b 243 c 264 ‘A^T^C) [1,3, 4, 6]

c 247 b 234 b 269 c 231 c 238 1 Alg—

1 T]u (Ci) [6,7]

c 239 b 229 b 265 c 227 c 235 l Alg^'Tlu (C2 ) [6,7]

c 232 b 225 b 262 c 224 c 232 'Alg^'Tlu (C3 ) [6,7]

b 164 a 133 b 167 b 187 a 230 b

1 76 c 220 (D) [3, 4, 7, 8]

a Room temperature.

b Liquid air/nitrogen temperature.

'Liquid helium temperature.

d Temperature between 4.2 and 77 K. References

[1] Fukuda, A., J. Phys. Soc. Japan 26, 1006 (1969).

[2] Fukuda, A., Inohara, K., and Onaka, R., J. Phys. Soc. Japan

19, 1274(1964).

[3] Zazubovich, G., Liidya, G. G., Luschik, N. E., and Luschik,

Ch. B., Bull. Acad. Sci. USSR Phys. Ser. 29, 380 (1965).

[4] Fukuda, A., Science of Light 13 , 64 (1964).

[5] Fukuda, A., Makishima, S., Mabuchi, T., and Onaka, R.,

J. Phys. Chem. Solids 28, 1763 (1967).

[6] Fukuda, A., J. Phys. Soc. Japan 27, 96 (1969).

[7] Fukuda, A., and Makishima, S., Phys. Letters 24A, 267

(1967).

[8] Inohara, K., Science of Light 14, 92 (1965).

10
Table 13. Optical absorption bands (in nm) of germanium centers

in alkali halides

Center NaCl KC1 KBr Assignment References

Ge2+ b 264 b 264 b 274 GGg-^TiJA) [1]

b 294 »Alg -»®Tl1l( Al) [2]

b 262 ‘Ajj—> 3Tlu(A2 ) [2]

b 222 b 222 b 226 1 Alg~J* X Tlu(C) [1]

b 230 M.l^Tl^Cl) [2]

b 219 ^ Ajg *

1

Ti u (C2) [2] — b 212 — 1 Alg ^'Tlu (C3 ) [2]

a Room temperature. c Liquid helium temperature.

b Liquid air/nitrogen temperature. d Temperature between 4.2 and 77K.

References

[1J Luschik, N. E., and Luschik. Ch. B.. Optics and Spectros- copy 8, 441 (1960).

[2]

Zazubovich, S. G., Luschik, N. E., and Luschik, Ch. B., Optics and Spectroscopy 15 , 203 (1963).

Table 14. Optical absorption bands (in nm) of bismuth centers

in alkali halides

Center KC1 KBr KI Assignment References

Bi3+ b 324 a 460 'Aly—» 3 Tlu(A) [1,2,3] — b 369 — » 3Tlu (Ax) [3] — b 359 — ^Ajg * ®Txu(A2 ) [3]

b 244 — — 1 Aig -^ 3 EU or 3 T2 u (B) [3]

b 220 — a 255 1 Axff —> ^^(C) [1,2]

b 212 b 233 — 1 Alg^ 'Ti u (Cx ) [3] b 207 b 224 — 'Axy-^TxutQ,) [3]

b 201 1 A19 -> 1 Txu(C3 ) [3]

b 194 b 211 — D' [3] Bi2 + a 335 — — [4] BiO + b 324 — — ‘Aij-* 3Txu(A) [3]

b 217 ^-^Ti^C,) [3]

b 207 — — 1 Alg ^'Tlu(C2 ) [3]

a Room temperature. c Liquid helium temperature.

b Liquid air/nitrogen temperature. d Temperature between 4.2 and 77K.

References

[1] Zazubovich, S. G., Luschik, N. E., and Luschik, Ch. B., Optics and Spectroscopy 15 , 203 (1963).

[2] Jain, S. C., Agarwal, S. K., and Chandra, G., (To be published).

[3] Siederdissen, J. Nonerzu, and Fischer, F.. Phys. Stat. Sol. 48, 215 (1971).

[4] Reisfeld, R., and Honigbaum, A., J. Chem. Phys. 48, 5565

(1968).

11

532-811 0 - 74 -3
Table 15. Optical absorption bands (in nrn) of thallium centers in alkali halides

Center NaCl NaBr Nal KC1 KBr KI RbCl RbBr Rbl CsCl CsBr Csl Assignment References

Tl1+ c 306 c 292 (Tl1+

) 2 [1]

c 303 c 289 (Tl1+

) 2 [1]

c 290 [2]

c 276 — [2]

e 257 [2]

b 253 b 268 b 291 b 245.8 b 258 b 281 b 242 h 258 c 280.5 a 247 c 256 — 1 Aly ^ 3 Tlu(A) [1. 2, 3,4, 5,6,

7, 8, 9, 10]

c 246 — [2]

d 247.3 ‘Au^TufA,) [3,4]

d 246.4 ‘A^-^T^A, As) [3]

d 245.8 ^y^T^A,) [3,4]

d 243.6 l Alg -^ 3 Tlu(As) [3,4]

c 263 c 250 B' [U — “ 260 b; [11] — — d 257 b; [11]

c 238 [2]

c 258 c 249 C' [1]

b 214 b 228 b 250 b 208 b 221 b 243.1 b 205 b 220 b 243 — c 242 — 1 Alf/ —

3 T2i/ or

3 E„(B)

[1, 2, 3, 4,5,7,

9, 11]

1. 199 b 218 b 238 c 194 b 208 b 232 b 197 h 208 b 234 a 196 c 225 — 'A.y^'TndC) [3, 4, 7, 8. 9, 11]

c 196.3 — c 234 1 Aly * 'Tlj/fCl ) [3,4,5]

e 194.4 c 232.8 1 A. 1 y * >Tl H (C2 ) [3, 4. 5]

c 192.8 e 232 1 A1 y-**T1B (C3 ) [3, 4, 5

b 161 b 188 ”224 b 169 b 190 c 223.9 b 174 b 198 b 226 D [5, 7, 10|

Tl° c 1470 c 1580 c 1695 2 P,/2-> 2 P.,/2 [12|

c 1300 c 1430 c 1550 2 Pl/2 —^ 2 P.i/2 [12]

b 640 [13]

h 380 [13]

b 300 [13]

b 250 — [13]

Tl2 ~ b 364 [13]

b 294 [13]

b 262 [13|

b 220 — [13|

a Room temperature.

h Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K. References

[lj Fukuda, A., J. Phys. Soc. Japan 26, 1006 (1969).

[2j Masunaga. S.. Morita. I., and Ishiguro. \L. J. Phvs. Soc. Japan 21, 638 (1966).

[3| Esser. P. D.. and Levy. P. W.. Int. Symp.. Color Centers in Alkali Halides. Rome. 1968. pp. 87.

[4] Stauber. M. C.. and Lemos. A. \L. Int. Symp. Color Centers

in Alkali Halides, Rome. 1968. pp. 264.

[5] Uchida. Y.. and Tsuboi. T.. J. Phys. Soc. Japan 24, 1075

(1968).

[6j Masunaga. S.. and Ishiguro. M.. J. Phys. Soc. Japan 25, 1337

(1968).

[7] Ramamurti. J.. Bull. Am. Phys. Soc. 14 , 357 (1969).

[8] Ghosh. A. K., J. Chem. Phys'. 43, 2978 (1965).

[9] Fukuda, A.. Science of Light 13 , 64 (1964).

[10] Inohara, K.. Science of Light 14 , 92 (1965).

[11] Matsui E.. J. Phys. Soc. Japan 22, 819 (1967).

[ 1 2 j Delbecq, C. J.. Ghosh A. K., and Yuster.P. H., Phvs. Rev. 154 , 797 (1967).

[13] Delbecq. C. J.. Ghosh, A. K., and Yuster, P. H., Phys. Rev. 151 , 599 (1966).

12
Table 16. Optical absorption bands (in nm) of tin centers in alkali halides

Center NaCl KC1 KBr KI RbCl RbBr Rbl Assignment References

Sn2+ b 294 b 288 b 312 1 Alg —> 3 Tllt (A1 ) [1]

b 285 b 279 b 305 ’

; — Ml 1 Ata —> 3 Tl„(A2 ) [1]

b 259 b 2'50 b 275 s — —teJL J — *Aig —> 3 E„ or 3 T2 u(B) [1]

b 239 b 237 b 260 b 300 b 239 b 264 1 Auj 'TiulCi) [12]

lX — '-SSBB

b 292 [2]

b 233 b 231 b 254 b 296 b 233 b 256 'Alg ~* 1 T] u (C2 ) [L2]

b 225 b 224 b 247 b 287 b 225 b 248 b 279 ‘AI9 -> 'T1U (C3 ) [1,2]

b 168 b 173 b 201 b 236 b 179 b 200 b 235 D' [L2]

b 160 b 165 b 190 b 222 b 173 b 194 b 224 D [1,2]

Sn“ b 387 b 420 T [3] t,

b 371 - _i: T [3]

b 294 b 317 j 4 — T [3]

b 265 b 279 Bglp _ ^ T [3] b 236 b 252 " - | I

j T [3]

b 223 b 238 l*L |

• T [3]

b 207 b 221

* -— T [3]

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K.

References

[lj Fukuda, A., Science of Light 13, 64 (1964)

[2] Inohara. K., Science of Light 14, 92 (1965)

[3] Velicescu, B., and Topa. V., Int. Conf. on Color Centers in Ionic Crystals, Reading U.K., 1971, Abs. No. D62.

Table 17. Optical absorption bands (in nm) of lead centers in alkali halides

Center NaCl Nal KC1 KBr KI RbCl RbBr Rbl CsCl CsBr Csl Assignment References

Pb2+ a 363 [1J

b 324 (Pb2+

)2 (A) [2]

b 271 -WWW b 270 b 297 b 353 ”270 b 302 b 358 a 278 a 310 a 373 >Aly -> 3 T,„(A) [1, 2, 3. 4, 5,6]

a 330 __ _ . t [1J

b 209 -J;

b 211 b 272 b 308 b 232 b 251 b 281 ! Aig —» 3 E« or 3 T2 u (B) [2. 3, 4, 6]

a 274 ' [1]

b 267 b 297 (Pb2+

) 2 (C') [2]

a 258 [1]

b 224 b 262 b 225 b 275 Ivly -> 'TdC) [2, 3, 5]

b 201 b 201 b 206 b 204 b 222 b 260 1 Ai„ ^ »T1U (C,) [3, 5, 6j

b 198 b 198 — — —

b 202 b 200 b 216 b 253 ‘Aly —> ‘Tj^C*) [3, 5, 6]

b 194 b 195 b 196 .] ^ — %*—

b 196 b 210 b 244 1 Al g

=* ’TiatCs) [3, 5, 6]

b 184 b 188 b 215 b 253 b 192 b 217 b 254 D' [3, 5]

b 160 b 165 b 192 b 228 b 173 b 194 b 229 — ---

b 215 D [5,6]

Pb1 + b— —

b 240 a 300 a 320 b 258 b 291 b 347 — [2,4,6]

Pb° b 604 (Pb°)2 [2]

a 285 b 280 [2,7]

C 1 - — r-

b 230 — [2]

13
Table 17. Optical absorption bands {in nm) of lead centers in alkali halides — Continued

Center NaCl Nal KC1 KBr KI RbCI RbBr Rbl CsCl CsBi Csl Assignment References

Pb Colloids a 270 — a 260 a 255 a 265 — [2,4]

Pb" b 447 b 564 b 497 b 541 b 608 T, [8, 9, 10]

b 418 b 490 h 444 b 460 b 502 t2 [8, 9, 10]

b 360 b 438 b 388 b 418 b 459 t3 [8, 9, 10]

b 332 b 359 b 383 b 427 t4 [8, 9, 10]

b 308 b 396 h 323 b 342 b 387 t5 [8, 9, 10]

h 284 b 365 b 296 t6 [8, 9, 10]

b 260 b 299 b 280 b 294 b 306 t7 [8, 9, 10]

b 239 b 257 b 274 b 301 t8 [8, 9, 10]

b 220 b 226 b 238 b 263 t9 [8, 9, 10] — — b 205 b 221 b 240 Tio [8, 9, 10]

Pb3+ b 465 [11]

b 303 [11] — — b 216 — [11]

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K. References

[1] Masunaga, S., and Ishiguro, M., J. Phys. Soc. Japan 25,

1337 (1968).

[2] Jain, S. C., Singh, Risal, and Agarwal, S. K.,(to be published).

[3] Fukuda, A., Science of Light 13,64 (1964).

[4] Jain, S. C., Radhakrishna, S., and Sai, K. S. K., J. Phys.

Soc. Japan 27, 1179 (1969).

[5] Inohara, K., Science of Light 14, 92 (1965).

[6] Pande, K. P., Ph.D. Thesis, I.I.T. Madras, India, 1972.

[7] Ikeda, T., and Yoshida, S., J. Phys. Soc. Japan 22, 138

(1967).

[8] Topa, V., and Velicescu, B., Phys. Stat. Sol. 33, K29

(1969).

[9] Billardon, M., Briat, B., Topa, V., and Taurel, L., Proc. XVI

Colloque. Symp. ‘Magnetic Resonances and Related Phenomena’ Bucharest, Romania (1970).

[10] Velicescu, B., and Topa, V., Int. Conf. on Colour Centres in Ionic Crystals, Reading U.K., 1971, Abs. No. D62.

[11] Schoemaker, D., and Kolopus, J. L., Solid State Comm. 8,

435 (1970).

Table 18. Optical absorption bands {in nm) of

titanium centers in alkali halides

Center LiF Assignment References

Ti a 270 [1]

a 250 [1]

a 240 [1]

a 207 — [1]

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K.

References

[1] Jain, S. C., and Sootha, G. D., Phys. Stat. Sol. 22, 505

(1967).

14
Table 19. Optical absorption bands (in nm) of

vanadium centers in alkali halides

Table 20. Optical absorption bands (in nm) of

chromium centers in alkali halides

Center NaCl Assignment 4 A29 References

V2+ b 1307 4 T2 (i2

) [1]

b 1242 4 T2 (r|) [1]

b 1221 4 T2 (t|) [1]

b 1215 4 T2 (f|) [1]

b 1190 4 T2 (t|) [1]

b 1169 4 T2 (i|) [1]

b 806 4 Tx(a) [1]

b 790 4 Ti(a) [1]

b 781 4Ti(a) [1]

b 772 4 Ti(a) [1]

b 762 4Ti(a) [1]

b 494 4 Tdb) [1]

b 236 Charge transfer [1]

b 200 Charge transfer [2] V1+ a 640 — [3]

Center NaCl KC1 Assignment References

Ci*~ b 330 [1]

b 240 b 240 — [1]

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K. References

[1]

Radhakrishna, S., and Sai, K. S. K., Phys. Stat. Sol. (b) 45,

K153 (1971).

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K. References

[1] Kuwabara, G., Phys. Rev. 138, A99 (1965).

[2] Kuwabara G., and Aoyagi, K., Japan. J. Appl. Phys. 4,

SuppL 1,627 (1965).

[3] Sai K. S. K., Ph.D. Thesis, I.I.T. Delhi. India. 1971.

Table 21. Optical absorption bands (in nm) of manganese centers in alkali halides

Center NaCl KC1 RbBr Assignment References

“A^S)-*

Mn2+ b 518 b 521 4Tx(G) [1]

b 460.5 b 443.5 : 4T2 (G) [1]

b 425.3 s [1]

b 421.6

b 417.5 J

b 418 — 4 Ai(G), 4 E(G) [1]

b 374 [1]

b 370.8 |

b 370.8

i

b 368.5 — 4T2 (D) [1]

b 353 b 354 4 E(D) [1]

b 326 b 332.5 4 TdP) [1]

b 274

b 262 }

a 272

f a 300

1

a 271 Charge transfer [2, 3]

b 255 a 260 4A2 (F), 4 Tx(F) [1]

a 245 a 255 Charge transfer [2, 3]

b 245.5 a 234 4 T2 (F) [1]

b 220 [3]

b 194 a 201 a 230 Charge transfer [2, 3] Mn+ b 278.5 3(/54s( 7 S)—» 3o(54p(7 P) [4] — a 223 — — [5]

15
Table 21. Optical absorption bands (in nm) of manganese centers in alkali halides — Continued

Center NaCl KCl RbBr Assignment

6 A , ( S) —

References

\ln° at the lattice site ‘ 422.8 [6]

c 415-226.5 [6]

c 226.5 — — — [6] Mn° at the off center ‘ 453.0 [61 position

‘ 408.4 [6]

' 355.9 [6]

c 415-226.5 [61

c 232.4 [6

c 226.0 [6 J c 216.7 — — — [61

Mn° at the interstitial site c 519.0 [61

1 453.0 [6]

c 389.3 [61

c 415-226.5 [61

c 232.4 [6]

c 226.0 [6 J c 216.7 — — — [6]

Mn° Aggregates a 210.0 a 210.0 — — [7J

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

(l Temperature between 4.2 and 77 K. References

[1] Mehra. A., Phys. Stat. Sol. 29. 847 (1968).

[2] Mehra. A., Japan. J. Appl. Phys. 7, 963 (1968).

[3] Kuwabara. G., and Aoyagi. K.. Japan. J. Appl. Phys. 4,

Suppl. 1. 627 (1965).

[4] Ikeva. M.. and Itoli. N., (Private communication).

[5] Mehendru. P. C., and Mitra. V., Phys. Rev. 176, 1089

(1968).

[6 ] Ikeya. M., and Itoh, N., J. Phys. Soc. Japan 29, 1295 (1970).

[7] Sootha. CL D., and Mitra, V., Physica 46, 531 (1970).

Table 22. Optical absorption bands (in nm) of cobalt centers in alkali halides

Center LiCl NaF NaCl NaBr KC1 KBr RbCl Assignment

4A 2 -* References

Co

2

* in tetrahedral b 1923 a 2070 4T i(F) [1,2]

symmetry

b 1727 a 1770 •T,(F) [1,2]

b 1493 a 1531 4T,(F) [1.2]

a 728 b 724 [3,4]

a 702 b 694 [3,4]

b 695 a 695 4T,(P) [L2J

b 660 a 667 4T,(P) [1,2]

b 640 a 630 4T,(P) [1,2]

8 668 b 670 [3]

a 644 b 640 [3.4|

b 610 b 625 b 608 [4,5]

b 599 b 602 b 580 [4,5]

b 585 [4, 5]

b 578 b 575 [4,5]

1 — — — b 552 b 562 b 568 — [4, 5] 16
Table 22. Optical absorption bands (in nm) of cobalt centers in alkali halides— Continued

Center LiCl NaF NaCl NaBr KC1 KBr RbCl Assignment

4A2 -* References

b 549 b 552 b 552 ___ [4,5]

b 544 b 540 b 542 [4,5]

b 535 b 535 b 535 [4.5]

a 529 d1 T, [1]

b 526 b 526 [4,5]

b 518 b 517 [4,5]

b 515 [4.5]

b 505 b 508 [4,5]

b 483 6

2

T> [1]

b 469 — [4]

b 457 b 462 b 453 [4,5]

b 454 b 450 [4. 5]

b 450 b

1 T, [1]

b 444 b 431 b 444 [4.5]

b 423 b 411 [4.5]

cr 4^O

-J [5]

a 271 [6]

a 244 [6] a 235 | [6]

a 230 [1] Co 2 ' in octahedral symmetry b 1412 [7]

b 1337 ___ | [7]

b 1312 [7]

b 1280 [7

b 967 [7]

b 615 b 610 ’ .. ^

' [4.7|

b 591 [4]

b 581 __ ___ [4] b 575 [4]

b 562 b 562 [4.8|

b 550 b 551 [4. 8|

b 543 . [4

b 538 [4]

b 535 b 533 b 533 [4.8]

b 523 b 526 b 525 [4.8]

b 518 [4|

b 515 b 515 b 507 b 516 [4. 7.8|

b 500 b 502 b 502 [7. 8|

b 465 b 495 [7. 8]

b 240 [9|

b 212 [9] — — b 193 — — — — [9]

Co+ — a 210 — a 212 — — — [10. 11|

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K. References

[1] Washimiya. S., J. Phys. Soc. Japan 18, 1719 (1963).

[2] Reynolds. M. L., Hagston. W. E.. and Garlick. G. F. J., Phys. Stat. Sol. 30, 97 (1968).

[3] Hills. M. E., J. Phys. Soc. Japan 19, 760 (1964).

[4] Musa. M., Phys. Stat. Sol. 16, 771 (1966).

[5] Musa. M., Phys. Stat. Sol. 9, K175 (1965).

[6] Mehra. A., Japan J. Appl. Phys. 6, 1030 (1967).

[7] Srivastava. J. P.. J. Chem. Phys. 48, 5283 (1968).

[8] Bohun. A., and Trutia. A., Phys. Stat. Sol. 9, K131 (1965).

[9] Cappelletti. R., Fieschi. R.. Martegani. G., and Pirola. L.

J. de Phys. 28, Suppl. C4-130 (1967).

[10] Jain. S. C.. and Lai. K.. Crystal Lattice Defects 1, 165 (1970)

[11] Jain. S. C.. Agarwal. S. K.. and Chandra. G., (To be pub

lished). 17
Table 23. Optical absorption bands (in nm) ofnickel centers in alkali halides

Assignment

Center LiF LiCl NaCl NaBr KC1 RbCl 3 A2ff—

References

Ni 2+ a 1233 — a 1850

a 1560 } ::: — — [1,2]

[1,2] — — a 1250 — — — — [1]

a 729 — a 935 — — — [1,2]

a 649 — a 792

a 771 }::: — — [1,2]

a 666 [1]

a 454 — a 545 — — — 1 T29 (D) [1,2]

a 405 — a 490

a 476 }::: — — [1,2]

a 254 a 266 [3]

a 246 a 265 3£ 2->eg( 3T2u ) [1] — a 254 a 242 a 321 a 251 — G(T**)-^c* [3] — a 207 a 216 a 280 a 220 — [3] — a 182 a 194 a 240 a 196 a 209 f 3ti u—> 3e ff ( 3T2 u)

1 e*-*a*u or t*u [1,3]

Ni + 350 370 [4] 310 340 [4] — — 279 — 288 — — [4]

a Room temperature.

bLiquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K. References

[1] Polak, K., Z. Physik 2 2 3, 338 (1969).

[2] Berge, P., Dubois, M., Blanc, G., and Adam-Benveniste, M.,

J. De Physique 26, 339 (1965).

[3] Nasu, T., and Asano, Y., J. Phys. Soc. Japan 27, 264 (1969).

[4] Kats, M. L., and Semenov, B. Z., Optics and Spectroscopy

4,637(1958).

Table 24. Optical absorption bands (in nm) of Table 25. Optical absorption bands (in nm) of

rhodium centers in alkali halides palladium centers in alkali halides

Center NaCl Assignment References Center NaCl KC1 Assignment References

Rh3+ a 680 'Aig-^Tig or 3 T2g [1] Pd2 + a 272 b 272 Charge transfer [1,2]

a 515 ’Alg—^'Tlg [1]

a 412 1 A- l(j~^ 'T 2g [1] Pd 1 + a 220 — Charge transfer [1]

a 250 Charge transfer [1]

a210 — [1] Pd Colloids — a 222 — [2]

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K.

aRoom temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K. Reference References

[1] Jain, S. C., Agarwal, S. K., and Sootha, G. D., Phys. Stat.

Sol. 40b, K69 (1970).

[1] Agarwal, S. K., Ph.D. Thesis, I.I.T. Delhi, India. (1970).

[2] Jain, S. C., Agarwal, S. K., Sootha, G. D., and Chander,

Ramesh, J. Phys. C. 3, 1343 (1970). 18
Table 26. Optical absorption bands (in nm) of europium centers in alkali halides

Center NaCl KC1 KBr KI Assignment References

Eu2 + d 410.8 \P~* 4f6 5d [U

_1 . §§

d 407.5 1 _ 4Z7 —» 4/6 5d [ 1 ] d 404.1 4/7 ^4/6 5(/ [ 1 ] d 400.8 4/7 —» 4/6 5e? [ 1 ] Ml d 397.5 -gT 4/7 ^ 4/6 5c/ [U

d 394.2 4/7 ^4/6 5J [U

_ d 391 — — — _ — 4/7^4/65(/ [U

d 388.5 § 4/7 —» 4/6 5d [11

d 386.4 4/7 ^4/6 5d [1J ESt. d 383.5 . 4/7 ^4/6 5rf [ 1 ] —

d 380.6 ___ 4/7-^4/65 J [U

d 376.8 b 375 4/7^4/65 rf [ 1 . 2] d 364 b 367 b 365 4/7 -^4/6 5 d [ 1 . 2 ] b 343 b 343 b 344.8 b 345 4/7 ^4/6 5d [2.3]

b 328.9 b 330 b 330 4/7^4/65 J [2.3]

i b 275 4/7 -^4/6 5(/ [ 2 ] b 270.6 b 270 4/

7 ^ 4/

65^ [2.3] d — b 260 4/7 —* 4/6 5d [ 2] b 249.2 b 249.2 b 254.3 b 255 4/7 —» 4/6 5d [2.3]

b 246.5 b 248.7 4/7 ^4/6 5d [3] b 240 b 243.1 4/7 —» 4/6 5g? [3.4]

b 234 b 235 4/7^4/65J [4]

Eu + a 570 [5]

b 400 — — — [ 6] a 312 [5]

a 272 — — — [5]

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K. References

[1] Bron. W. E., and Wagner, M., Phys. Rev. 145, 689 (1966).

[2] Verenko. G. D., et al.. Optics and Spectroscopy 28, 36 (1970).

[3] Reisfeld, R., and Glasner, A., J. Opt. Soc. Amer. 54 , 331

(1964).

[4] Chowdri, B. V. R., and Itoh. N., Phys. Stat. Sol. 46, 549

(1971).

[5] Parfianovich, I. A., et al.. Bull. Acad. Sci. USSR: Phys.

Series 30, 1479 (1966).

[6] Gorobets, B. S., et al., Sov. Phys. Dokl. 13, 519 (1968).

Table 27. Optical absorption bands (in nm) of samarium centers in alkali halides

Center NaCl Nal KC1 KBr KI RbCl Assignment References

Sm2+ d 627.2 c 662.3 c 613 c 614 d 629 d 605 4/6 ^ 4/55e? [1.2.3]

J3

c 584.8 d 569.8 ___ 4/

6 ^ 4/

55 ^ [ 1 . 2 ] c 542.3 c 541.8 c 544.9 4/

6 ^ 4/55d [1.2.3]

c 504.6 c 504 =* ' - 4/

6 ^ 4/55d [1.2.3] — e 458.5 — — yBSuS _ 4/6 —» 4f55d [2 ] —

c 432 c 431.5 c 432.9 ^

’ 4/

6 ^ 4/55d [1.2.3] — c 408 c 408 4/

6 ^ 4/

55^ [1.2.3] — c 382 d 387.4 4/

6 ^ 4/

55^ [ 1 . 2 ] c 371 — — 4/6 —» 4f55d [2 ] e 337.7 c 358 4/6 —» 4/55<i [1.2.3]

c 327.5 c 344.9 4/6^4/55^ [1.2.3] — d 275.5 4/6^4/55^ [1.3] — — d 268.4 — — 1

— 4/6 —> 4f55d [1.3]

19

532-811 0 - 74 -4
Table 27. Optical absorption bands (in nm) of samarium centers in alkali halides — Continued

Center NaCl Nal KC1 KBr KI RbCl Assignment References

cl 261.4 ___ ___ 4/6 ^4/5 5d [1.3] — — “249 — — — 4/B —» 4/5 5d [1.3] — — “241 — — 4/6 ^4/55rf [1.3] — — “225.5 — — — 4/6 —»• 4/55<7 [1-3] — — CO CO — — — — 4/6 ^ 4/56s 1 [3] — — “173 — — — 4/6 ^ 4/56s 1 [3] Sm^ b 1250 6H5/2 [4] b 1120 6h7/2 [4]

h 961.6 6h9/2 [4]

h 861.1 6h„/2 [4] — — h 799 2 — — 6Hi3/ 2 [4]

a Room temperature b Liquid air/nitrogen temperature.

c Liquid helium temperature. d Temperature between 4.2 and 77 K. References

[1| Bron. W. E., and Heller. W. R., Phys. Rev. 136A, 1433 (1964). [3) Patscheke. E., Z. Physik 186, 63 (1965).

[ 2 ] Kaplyanskii. A. A., et al.. Optics and Spectroscopy 16, 144 [4) Fong. F. K., et al., Phys. Rev. 151, 299 (1966). (1964).

Table 28. Optical absorption bands (in nm) of holmium centers

in alkali halides

Center KC1 KBr Assignment References

Ho2 + b 310 b 299 4/11-^4/105^ [11

b 269 b 260 4/

11 ^ 4/

105^ [11

11 245 ”225 4/n—> 4/105^ [11

b 234 b 216 4/

11 ^ 4/

105^ [11 Ho+ a 375 [11

a 282 , [11 — a 252 — [ 1 ]

Ho° — a 220 Clusters of Ho° [11

a Room temperature.

11 Liquid air/nitrogen temperature.

'Liquid helium temperature.

'‘Temperature between 4.2 and 77 K. Reference

[1 1 Sai. K. S. K.. Ph.D. Thesis. I.I.T. Delhi. India (1971).

20
Table 29. Optical absorption bands (in nm) of ytterbium centers in alkali halides

Center NaCl KC1 KBr Assignment References

Yb

2

+ d 377.3 [1]

d 337 [1] b 310 b 300 [2]

b 270 b 270 [2] — b 245 [2]

B*

b 230 b 225 — [2] Yb3+ b 270 b 270 — [3]

3 Room temperature. b Liquid air/nitrogen temperature.

c Liquid helium temperature. d Temperature between 4.2 and 77 K. References

[1] Wagner. M., and Bron. W. E., Phys. Rev. 139,223(1965). [3] Sootha. G. D., Tripathi. T. C.. and Agarwal. S. K.. Phys.

[2] Dolgopolova. A. V., et al.. Optics and Spectroscopy 17, 73 Stat. Sol. 44b. K61 (1971). (1964). Table 30. Optical absorption bands (in nm)

of uranyl centers in alkali halides

Center LiF NaCl KC1 Assignment References

uo2 - b 290 b 260 b 270 [1.2]

b 240 — b 234 — [11

a Room temperature. h Liquid air/nitrogen temperature.

c Liquid helium temperature. d Temperature between 4.2 and 77 K. References

[1J Sootha. G. D.. Radharkrishna. S.. and Agarwal. S. K.. Xuovo [2] Agarwal. S. K.. Ph.D. Thesis. I.I.T. Delhi. India. 1970. Cimento 64B. 19 (1969).

Table 31. Optical absorption bands (in nm) of hydrogen centers in alkali halides

Center NaF NaCl NaBr Nal KC1 KBr KI RbCl RbBr Rbl CsBr Csl Assign- mentRefer- ences

U(H-) a 157 192 210 A

d 211.5 d 225 244 d 226 242 d 242.5 d 269 — [1. 2. 3. 4.5]

U(D-) — — — — d 210.8 d 224 * 't d 225.3 ——

d 268.5 — [3.5]

U, d 220 d 259 d 328 d 235 d 272 d 337 d 247 d 280.5 d 345 — — — [61

u; — — d 242.5 d 300 — d 257 d 315 — d 267 d 325 - — — [6]

U" — — d 217 d 255.5 — d 240.5 d 266.5 — d 251.5 d 272.5 — — — [61

a Room temperature. b Liquid air/nitrogen temperature.

c Liquid helium temperature. d Temperature between 4.2 and 77 K. References

[1] Meistrisch. M. L.. J. Phys. Chem. Solids 29, 1119 (1968).

[2] Schulman. J. H.. and Compton. W. D.. Color Centers in Solids. Pergamon Press. N.Y. (1962).

[3] Baldini. G.. Mulazzi. E.. and Terzi. N.. Phvs. Rev. 140,

A2094 (1965).

[4]

Mitra. S. S.. and Brada. Y.. Phys. Rev. 145, 626 ( 1966 >. [6] Tanton. G. A.. Shatas. R. A.. Singh. R. S.. and Mitra. S. S,

J. Chem. Phys. 52, 538 (1970).

[6] Fischer. F.. Z. Physik 204, 351 (1967).

21
Table 32. Optical absorption bands (in nm ) of

halogen centers in alkali halides

Center NaBr KC1 KBr Assignment References

I" b 193.5 b 184.7 b 193.8 — [1,2]

a Room temperature. b Liquid air/nitrogen temperature.

c Liquid helium temperature. d Temperature between 4.2 and 77 K. References

[1]

B. W. Fowler, “Physics of Colar Centers,” Ed B. W. Fowler, [2] Rolfe, J., Appl. Phys. Letters 6,66(1965).

Academic Press (1968), pp 53-179.

Table 33. Optical absorption bands (in nm) of

oxygen centers in alkali halides

Center NaF NaCl KC1 KBr Assignment References

Or b 248 b 248 b 248 [1] 142 — 194 — — [2, 3]

a Room temperature. b Liquid air/nitrogen temperature.

c Liquid helium temperature. d Temperature between 4.2 and 77 K. References

[1]

Rolfe, J., Lipsett, F. R., and King, W. J., Phys. Rev. 123,

447 (1961).

Table 34. Optical absorption bands (in nm) of

sulphur centers in alkali halides

Center KC1 KBr Assignment References

SH- b 185.1 b 193.6 — [1,2,3]

s- b 192.4 b 203.5 — [1,2,3]

S-- b 393.5 — — [2]

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K. References

[1] Fischer, F., and Grundig, H., Phys. Letters 13, 113 (1964).

[2] Fischer, F., and Grundig, H., Z. Physik 184, 299 (1965).

[3] Rolfe, J., Appl. Phys. Letters 6,66 (1965).

[2] Meistrisch, M. L., J. Phys. Chem. Solids 29, 1119 (1968).

[3] Fischer, F., Grundig, H., and Hilsch, R., Z. Phys. 189, 79

(1966).

TABLE 35. Optical absorption bands (in nm) of

selenium centers in alkali halides

Center KC1 KBr Assignment References

SeH~ d 202.4 d 211.4 [1]

d 193.6 d 202.3 — [1]

Se~ d 208.6 d 2l9.0 [1]

d 201.6 d 212.6 — [1]

Se~

- d 395 d 406.5 [1]

d 364 d 374 — [1]

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K. Reference

[1] Fischer, F., Z. Physik 187, 262 (1965).

22
Table 36. Optical absorption bands (in nm) of OH/OD centers in alkali halides

Center NaF NaCl KCl KBr Assignment References

OH- 151.2 b 185 c 205 b 214 [1.2. 3. 4] OD- H— d 203 — —1 {t [4]

a Room temperature. b Liquid air/nitrogen temperature.

c Liquid helium temperature. d Temperature between 4.2 and 77 K. References

[1] Meistrisch. M. L., J. Phys. Chem. Solids 29 , 1119 (1968). [3] Sittig. R., Phys. Stat. Sol. 21 , K175 (1967).

[2] Etzel, H. W., and Patterson. D. A., Phys. Rev. 112 , 1112 [4] Fischer, F., Sol. Stat. Comm. 2,51 (1964).

(1958). Table 37. Optical absorption bands (in nm) of amide centers in alkali halides

Center KCl KBr KI Assignment References

nh2- d 253.9 d 272.2 d 295.0 o-o [1] nd2- d 251.8 d 268.5 d 294.0 o-o [1]

a Room temperature b Liquid air/nitrogen temperature.

c Liquid helium temperature. d Temperature between 4.2 and 77 K. References

[1] Windheim, R., and Fischer, F., Z. Physik 197, 309 (1966).

Table 38. Optical absorption bands (in nm) of nitrite centers in alkali halides

Center NaBr KCl KBr KI Assignment References

N02- * c 397.2 * c 398.8 * c 401.1 * e 401.1 Zero-phonon transition [1.2]

*This band shows vibrational progression with separations b Liquid air/nitrogen temperature.

(~ 1010 cm-1 and 600 cm-1

) . c Liquid helium temperature.

a Room temperature. d Temperature between 4.2 and 77 K. References

[1] Timusk, T., and Staude, W., Phys. Rev. Letters 13 , 373 [2] Avarmaa, R., and Rebane, L., Phys. Stat. Sol. 35 , 107

(1964). (1969). Table 39. Optical absorption bands (in nm) of chromate centers in alkali halides

Center KCl KBr KI Assignment References

CrO|- * b 335 * b 355 * b 365 h—>e [L2] — b 285 _ [1.2]

b 270 b 270 b 270 ti r2 [1.2]

b 240 b 246 — [1.2]

This absorption band shows a vibrational progression with b Liquid air/nitrogen temperature,

a separation of 800 cm-1

. The peak position reported here corc Liquid helium temperature,

responds to the strongest peak in the progression. d Temperature between 4.2 and 77 K.

a Room temperature.

References

[1] Jain, S. C., Warrier, A. V. R., and Agarwal, S. K., Chem. [2] Jain, S. C., Warrier, A. V. R., and Agarwal, S. K., J. Phys.

Phys. Letters 14 , 211 (1972). Chem. Solids 34 , 209 (1973). 23
Table 40. Optical absorption bands [in nm) of

permanganate centers in alkali halides

Center KBr KI Assignment References

MnO}- * c 600 * c 650 t\ —> e [1.2|

* c 520 * c 540 t\—*e [1.2|

c 390 t-2 e [11

c 336 to e [11

e 305 — [U

c 230 h h [U

c 200 — — [1]

*These bands show vibrational progression with separations

of 760 cm -1 and 780 cm -1

. The peak position corresponds to the strongest peak in the progression.

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K. References

[1] Jain. S. C.. Pooley. D.. and Singh. Risal. J. Phys. C. 5, L307 [2] Jain. S. C., Singh. Risal. and Agarwal S. K., (to be published).

(1972).

Table 41. Optical absorption bands {in nm) of manganate centers

in alkali halides

Center KC1 KBr KI Assignment References

MnOj- b 850 b 850 b 850 e —> to [11 * b 600 * b 600 " b 600 e [1.2)

b 430 b 430 b 430 t\ -> to [2]

b 340 b 340 b 340 t\ ~> t-i [21

b 290 b 290 b 290 t\ ~> to [21

*This band shows vibrational progression with a separation

of 740 cm -1

. The peak position given here corresponds to the

strongest peak in the progression.

a Room temperature.

h Liquid air/nitrogen temperature.

c Liquid helium temperature.

‘'Temperature between 4.2 and 77 K. References

[1| Jain. S. C.. Singh. Risal. and Agarwal. S. K.. (to be published). [2| Jain. S. C., Sootha. G. D., and Agarwal. S. K., J. Phys.

Chem. Solids 32, 897 (1971).

24
Table 42. Optical absorption bands (in nm) offerricyanide

centers in alkali halides

[1] Jain. 6 .

[1] Jain. 5 ,

Center NaCl KC1 Assignment References

Fe(CN)3- a 505 a 500 tlge

lg

(. AT„) [1]

a 420 a 414 t\Ag O T,.) [1]

a 376 a 377 [1]

a 357 a 348 tige^g) [1]

a 338 a 323 ti9e\{ 2A2s, 2Ti9 ) [1]

a 302 a 296 n&ge\ [U

a 262 a 274 [1] _ — a 258 If tf [1] — a 248 If pl

£ lu £ 20C

g [1] — a 200 tf P £1 L iuL2srg [1]

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K.

References

S. C.. Warrier. A. V. R.. and Sehgal. H. K., J. Phvs. C. 193 (1973).

Table 43. Optical absorption bands (in nm) ofcobalticyanide

centers in alkali halides.

Center NaCl KC1

Assignment

tSgOAl,)- References

Co(CN)§- a 484 a 480 ti9eg( 3 T lg) [1]

a 409 a 400 ti»eJ( 3 T2ff ) [U

a 361 a 353

a 316 a 310

('Tjg) [1]

a 280 a 277 [11

a 260 a 258 — a 201 ^1M [1]

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K. Reference

S. C.. Warner. A. V. R.. and Sehgal. H. K., J. Phvs. C. 1511 (1972).

25

PART II.

Vibrational Frequencies of Internal Modes of

Complex Ions Doped in Alkali Halide Crystals

27
.
Table 44. Point group symmetry, normal modes and their activity in infrared

absorption and Raman scattering for the molecular ions investigated.

No. of atoms

Point group symmetry

Modes and their symmetry and

activity in infrared and Raman 3 Molecular impuritiesinvestigated

2 D,h ^ (2£;R) Nr, Of, Sf, Ser

2 c xv vt (1~; IR. R) OH-, OD-, CN-, SH-, SeH-,

SSe3 D,h t'ls (2+; R)

v2 b (n u ; IR)

*3* (2l;IR)

N3 .BO 7

3 c xv vis (2"; IR. R)

V2b (II; IR R)

v3s (1~; IR. R)

NCO-. NCS3 c 2v vis (Ai; IR. R)

^2b(Ai; IR. R)

^3s (B2 ; IR. R)

NO 9 . NHa, NDi, H2 0 NHDs3

4 C 3v ^is (Ai, IR, R)

^2b(Ai; IR. R)

^3s (E, IR. R)

i'

b (E: IR. R)

CIO 3

, IO 3-. SeOf4 D3h ^i s (A';R)

^2b (A"; IR)

^3s (E'; IR. R)

*4b(E': IR. R)

NO-, CO*-. B03-

5 Td vls (Ai; R)

i^ 2b (E; R)

v3s (T 2 ; IR. R)

^4b (T 2 ; IR. R)

NH+, ND+, BH7

. BDj. BF;. CIO 7

. MnO", SO*", SeO^-.

CrO*“. MnO*", MoO*-,

BeF^ -

13 oh ^is(Aiff ; R)

V3S (Eff ; R)

^65 (Tiu; IR)

Co(CN)*-, Co(CN)|-,

Co(CN)*-, Fe(CN)*-,

Fe(CN)J- Fe(CN)JSubscripts ‘s’ and ‘b’ for the modes indicate stretching and bending respectively. IR and or R in the parenthesis after the modes means whether that particular mode is infrared and or Raman

active.

29
Table 45. Internal vibration frequencies of homonuclear diatomic molecular ions doped in alkali

halide crystals.

These ions have only one vibrational mode vs

( V j which is Raman active and infrared inactive. The accuracy, when given by

' sr the authors, is quoted. In other cases the accuracy is estimated to be ± 1 cm -1

, except in the cases marked with an asterisk where no

idea of accuracy could be obtained. The values have been rounded off to nearest wavenumber unless the accuracy is equal to or better than ±0.5 cm -1

. ESR and uniaxial stress experiments 1 suggest that Oy, Sf and Sef are aligned along (110) direction in FCC alkali halides.

Crystal : Impurity Frequency (cm x

) -(s) ' a'

Temperature

K

Remarks References

KC1 : N2- 1836 ±3 RT Raman [2] KBr : Nf 1821 ±3 RT Raman [21 KI : Nf 1870 ±3 RT Raman [2]

NaCl : 02- 1144 ±1 RT Raman [2.3.4|

NaBr : Of 1131 ±1 RT Raman [2. 3. 4] KC1 : Of 1145 ±1 RT Raman [2.3.4|

KBr : Of 1135 ± 1 RT Raman [2. 3. 4| KI : Of 1123 ± 1 RT Raman [2. 3. 4|

RbCl : Of 1141 ±1 RT Raman [2. 3. 4|

RbBr : Of 1132 ±1 RT Raman [2. 3. 4|

NaBr : Sf 610 ± 1 RT Raman [21 Nal : Sf 592 ±1 RT Raman [21 KBr : Sf 612 ±2 RT Raman [2

KI : Sf 594 ±1 RT Raman [2) RbBr : Sf 611 ± 1 RT Raman [21 Rbl : Sf 598 ± 1 RT Raman [21

Nal : Sef 333 ±1 RT Raman [2

KI : Sef 325 ±1 RT Raman [2

RT — Room temperature.

References

[lj Zeller. H. R.. and Kanzig. W.. Helv. Phys. Acta 40, 845

(1967).

[2| Holzer. W.. Murphy. W. F.. and Bernstein. H. J.. J. Mol.

Spect. 32, 13 (1969).

[3| Holzer. W.. Murphy. W. F.. Bernstein. H. J.. and Rolfe. J.. J. Mol. Spect. 26,543 (1968).

[4 1 Rolfe. J.. Holzer. W., Murphy. W. F., and Bernstein. H. J.. J. Chem. Phys. 49, 963 (1968).

30
Table 46. Internal vibrational frequencies of heteronuclear diatomic molecular ions in alkali halides.

These ions have only one vibrational mode vs (1 + ) which is both Raman and IR active. The accuracy, when given by the authors,

is quoted. In other cases the accuracy is estimated to Bert 1 cm-1

, except in the cases marked with an asterisk where no idea of accuracy

could be obtained. The values have been rounded off to nearest wavenumber unless the accuracy is equal to or better than ±0.5 cm -1

. Stress and dichroism experiments suggest that the molecular axis in the (100) direction for CN~ and perhaps also for OH -

in FCC

alkali halides 1 and (110) or possibly (111) in BCC alkali halides 3

. The free ion frequencies are:

vs = 3596 cm -1 for OH-

, v = 2680 cm -1 for OD - and vs = 2042 cm 'forCN .

Crystal : Impurity Frequency (cm -1

) r,(2j)

Temperature

K

Remarks References

NaCl:CN- 2106.8 10 Raman [2] NaBr:CN- 2087 ± 1 100 IR [3] NalrCN- 2074 ±1 100 IR [3] KC1:CN- 2087.7 8.5 Raman [2] KBr:CN- 2078 2 IR [4] KI:CN- 2067 2 IR [4] RbClrCN- 2081 2 IR [4] RbBr:CN- 2070 ±1 100 IR [3] RbI:CN~ 2063 ± 1 100 IR [3] CsCLCN- 2078 ±1 100 IR [3] CsBr:CN- 2066 ±1 100 IR [3]

CsI.CN- 2053 ± 1 100 IR [3] NaCl:OH- 3654.5 ± 0.5 4.5 IR [6] NaBr:OH- 3626 ±0.5 4.5 IR [6J KCl:OH- 3641 ±0.5 4.5 IR [6] KBr:OH- 3618 ±0.5 4.5 Raman and IR [5.6] KI:OH- 3603 4.5 IR [6] RbCLOH- 3632 ± 0.5 4.5 IR [6] NaCl.OD- 2689 4.5 Raman [5] KCl:OD- 2684.5 ±0.5 4.5 IR [6. 7J KBr:OD- 2668 ±0.5 4.5 IR [6] KCLSH- *2585 RT IR [8] KBr:SH- *2569 RT IR [8] KCLSeH- *2294 RT IR [9]

Nal : SSe- 462 ±1 RT Raman [10] KI:SSe- 464 ±1 RT Raman [10] RT Room temperature.

References

[1] Narayanamurti. V.. and Pohl. R. O., Rev. Mod. Phys. 42,

201 (1970).

[2] Callender, R. H.. and Pershan. P. S., Light Scattering

Spectra of Solids. Ed. G. B. Wright. Springer-Verlag. N.Y., pp. 505-12 (1969).

[3] Field, G. R.. and Sherman. W. F., J. Chem. Phys. 47,

2378 (1967).

[4] Seward. W. D.. and Naravanamurti. V.. Phys. Rev. 148 , 463 (1966).

[5] Fenner. W. R.. and Klein. M. V.. Light Scattering Spectra

of Solids. Ed. G. B. Wright. Springer-Verlag. N.Y.. pp. 497-504 (1969).

[6] Wedding. B.. and Klein. M. V., Phvs. Rev. 177 , 1274

(1969).

31
[7| Chau. C. K.. Klein. M. V.. and Wedding. B.. Phys. Rev.

Letters 17,521 (1966).

[8 1 Rolfe. J., Appl. Phys. Letters 6, 66 (1965).

[9) Fischer. F.. Z. Phys. 187, 262 (1965).

[10] Holzer. W.. Murphy. W. F.. and Bernstein. H. J.. J. Mol.

Spect. 32, 13 (1969).

TABLE 47. Internal vibrational frequencies (cm J ) of linear triatomic molecular ions with Dx h point

group, doped in alkali halides.

These ions have one mode v\

y s

) which is only Raman active and two modes v> ( b I and s

) only infrared active. The accuracy, when given by the authors, is quoted. In other cases the accuracy is estimated to be ± 1 cm ~ except in the cases marked

with an asterisk where no idea of accuracy could be obtained. The values have been rounded off to nearest wavenumber unless the accuracy is equal to or better than ±0.5 cm -1

, N.-f and BOy enters substitutionally into the lattice at the anion site such that molecular

axis is along (111) in FCC alkali halides [1, 2]. The free ion values are known only for Nj ions and are i' t = 1344 cm -1

, v-i — 645 cm -1 and ^3 = 2041 cm -1

Crystal : Impurity

Frequency (cm

Temperature

K

Remarks References

-(s)9 *(ri) N u»(t) x U

'

NaCl : N3- 640.3 ±0.1 2083.1 ±0.1 120 IR [1] NaBr : N.r* 2064.5 IR [2] Nal : N;f* 2037.0 IR [2] KC1 : N3- 643.0 ±0.1 2051.2 ±0.1 120 IR [1] KBr : N3~ 641.5 ±0.1 2038.2 ±0.1 120 IR [11 KI : Ns" 639.7 ±0.1 2022.1 ±0.1 120 IR [1] RbCl :N3~* 2040.0 IR [2] RbBr : N.-T* 2029.0 IR [2] Rbl : Ns"* 2016.2 IR [2] CsCl : Ns * 2043.0 IR [2] CsBr :Ns* 2026.0 IR [2] Csl :Ns* 2006.0 IR [2] KC1 : BOf

10B,6O16 O 610 2043 IR [3]

,0B

16 O17O 2038 IR [3]

,0B

l6O18O 2029 IR [3] nB.16016 0 590 1972 IR [31 "B l6 0,7 0 1968 IR [3] "B1B 0,8 0 — — 1959 — IR [31

KBr : BO-f

loB

160,60 607 2029 IR [31

IOB

16 0,7 0 2023 IR [31 "*B ,6 Oih O 2016 IR [31

1

B

IK 0Ifi 0 587 1959 IR [31 "Blfi Ol7 0 1953 IR [3] n B

i«0 ,K 0 — — 1946 — IR [31

KI : BOs"

,0B

,6O16 O 607 2016 IR [4]

,0 B

16 O,8O 2000 IR [41 "Bie O,60 — 587 1946 — IR [41

References

[1] Bryant. J. I., and Turrell, G. C., J. Chem. Phys. 37, 1069

(1962).

[2] Price, W. C., Sherman, W. F., and Wilkinson, G. R., Spectrochim. Acta 16,663 (1960).

[3] Morgan, H. W., and Staats, P. A., J. Appl. Phys. 33, 364

(1962).

[4] Mauring, T., Eesti NSV Teaduste Akadeemia Toimetised

XVII Koide, Fuusika, Mathemaatika (1968) NR.2. 232-234. 32
Table 48. Vibrational frequencies of triatomic linear molecular ions doped in alkali halides.

These ions have three modes, fi(2 +

), v3 (11) and v3 {1^) which are both Raman and infrared active. The accuracy, when given

by the authors, is quoted. In other cases the accuracy is estimated to be ± 1 cm -1

, except in the cases marked with an asterisk where

no idea of accuracy could be obtained. The values have been rounded off to nearest wavenumber unless the accuracy is equal to or

better than ±0.5 cm -1. NCO - and NCS - enter the alkali halide lattice substitutionally replacing the anion such that the molecular

axis is along (111) in FCC alkali halides [1] and along (100) in BCC alkali halides [5], The free ion frequencies are:

1^1 = 1207 cm

1

, vo — 637, 628 cm 1 and v3 = 2165 cm 1 for NCO

and v x =743 cm -

, v> = 470 cm -

and v3 = 2066 cm -1 for NCS -

.

Crystal : Impurity

Frequency (cm x ) Temperature

K

Remarks References

ms+

) Mri) ^a(2

+

)

NaCl : NCO -

14N 12 C

16 0

- 633.2 ±0.3 2211.2 ± 0.3 298 IR [1]

14 N 13 C

16 0

- — — 2153.1 ±0.3 298 IR [U

NaBr : NCO - 1217.6 637.3 2219 — IR [2]

Nal : NCO - 1210.6 636.4 2195 — IR [2]

KC1 : NCO -

14 N12 C

16 0

- 1211 2182 100 IR [4]

14 N13 C 16 0

- — 613.2 ±0.3 2153.1 ±0.3 298 IR [1] KBrrNCO -

14 N12 C

16 0

- 1206 629.98 2170 100 IR [3.4]

14 N 13 C

lfi O

- 612.78 2115 100 IR [31

15 N12 C 16 0- 626.64 2154 100 IR [3]

14 N 12 C 18 0

- 625.23 2163 100 IR [3J

14 N13 C,8 0

- 2104±0.3 298 IR [11

15 N13 C16 0

- 2097 100 IR [31

15 N12 C 18 0

- 1— — 2144 100 IR [3]

KI : NCO -

14 N 12 C16 0

- 1200.8 ±0.3 628.0 ±0.3 2155.8 ±0.3 298 IR [11

14 N 13 C16 0

- 610.0 ±0.3 2099.0 ±0.3 298 IR [1]

14 N 12 C18 0

- 2148.2 ±0.3 298 IR [1]

15 N12 C 16 0

- T < — 2138.7 ±0.3 298 IR [11

RbCl : NCO - 1211.8 635.1 2201 IR [2] RbBr : NCO - 1207 633.5 2191 IR [21 Rbl : NCO - 1202.4 632.4 2179 IR [2] CsCl : NCO - 1212.4 633.2 2205 IR [21 CsBr : NCO - 1206 632 2187 IR [2] Csl : NCO - 1200 630 2170 — IR [2]

Nal : NCS - * 2050 40 IR [51 KI : NCS - * 2038 40 IR [51 Rbl : NCS - * 2028 40 IR [51 Csl : NCS - * — — 2038 40 IR [51

References

[1] Maki. A., and Decius, J. C., J. Chem. Phys. 31, 772 (1959).

[2] Price. W. C., Sherman, W. F., and Wilkinson, G. R.. Proc. Roy. Soc. A255, 5 (1960).

[3| Decius. J. C.. Jacobson. J. L., Sherman. W. F., and Wilkinson,

G. R.. J. Chem. Phys. 43, 2180 (1965).

[4] Conant, D. R., and Decius, J. C., Spectrochim. Acta 23A,

2931 (1967).

[5] Cundill, M. A., and Sherman, W. F., Phys. Rev. 168, 1008

(1968).

33
Table 49. Vibrational frequencies (cm *) of bent triatomic molecular ions doped in alkali halides.

These ions have three modes i/i(Ai), 1^2 (A 1 ) and 1/3(62) which are both Raman and infrared active. The accuracy, when given

by the authors, is quoted. In other cases the accuracy is estimated to be ± 1 cm -1

, except in the cases marked with an asterisk where

no idea of accuracy could be obtained. The NO-r ion enters substitutionally into the lattice at the anion site such that the 2-fold axis of the ion points in the (110) directions in FCC alkali halides. The values have been rounded off to nearest wavenumber unless the accuracy is equal to or better than ±0.5 cm-1

. The free ion values are:

v\ = 1328 cm-1

, v2 — 828.2 cm-1 and j/3 = 1261 cm-1 for NOf

i/i = 3210 cm-1

, v2 = 1532 cm -1 and 1/3 = 3266 cm'

1

for NH2-

v\ — 2355 cm-1

, p2 = 1131 cm-1 and 1/3 = 2429 cm-1 for NDf

j/i = 2387 cm"1, p2 = 1247 cm -1 and p3 = 3236 cm-1 for NHD" and

1/1 = 3657 cm -1

, p2 — 1595 cm -1 and p3 = 3756 cm-1 for H2 0.

Crystahlmpurity

Frequency (cm 1 ) Temperature

K

Remarks References

^i(Aj) (Aj ) v3 (B2 ) NaCLNOr 1346 636 1304 2 IR [1]

NaBr:N02- 1327 ±2 828 ±2 1283 ±2 6 R [2] KCLNOf 1329 805 1290 2 IR [1] KBr:N02-

14N1602~ 1316. 2±0.

798.1 ±0.5 1275 ±0.5 8 IR [31

14N160180“ 1303.9 ±0.5 779 ±0.5 1256.6 ±0.5 8 IR [31

15Nlfi0160- 1294.2 ±0.5 793 ±0.5 1249.5 ±0.5 8 IR [31

15N16018Cr 1230.4 8 IR [3

15N180180

_ — — 1221.5 8 IR [3]

KI:N02- 1308 806 ±2 1253 5 IR [11

NaCLSa" 531 ±1 300 IR, R [4

NaBr:S.f 523 ±1 300 IR, R [41 KCl:S.f 527 ±1 540 ±2 300 IR, R [4

KBr:S.f 523 ±1 585 ±2 300 IR, R [4

KLS3- 543 ±1 585 ±2 300 IR, R [41 RbCl:S3- 528 ±1 300 IR, R [41 RbBr:S3- 555 ±1 300 IR, R [4|

RbI:S3- 544 ± 1 — 300 IR, R [41 KC1:NH2- 3202 1532 3258 20 a IR [51 KBr:NH2- 3185 1508 3235 20 a IR [51

KI:NHr 3154 1500 3202 20 a IR [51 KCLNHD" 2379 1355 3218 20 a IR [5] KBr:NHD- 2371 1330 3202 20 a IR [5] KCLNDr 2353 1137 2419 20 a IR [5] KBriNDf 2339 1121 2412 20 a IR [5] KI:NDf 2323 1113 2395 20 a IR [5]

KC1:H2 0 3435 1630 3400 20 IR [6] KBr:H2 0 3472 1625 3425 20 IR [6] KI:H20 3570 1690 3390 20 IR [6]

a The absorption maxima expressed in eV in the paper is converted to wave number (cm ') by using the conversion factor 1 eV = 8065 cm-1

. References

[1] Narayanamurti, V., Seward, W. D., and Pohl, R. O., Phys. Rev. 148,481 (1966).

[2] Evans, A. R., and Fitchen, D. B., Phys. Rev. B2, 1074

(1970).

[3] Rolfe, J., J. Chem. Phys. 47, 1901 (1967).

[4] Holzer, W., Murphy, W. F., and Bernstein, H. J., J. Mol. Spect. 32, 13 (1969).

[5] Windheim, R., and Fischer, F., Proc. Int. Conf. ‘Luminescence’, Budapest (1966) pp. 877-882.

[6] Ruhenbeck, C., Z. Phys. 2 0 7, 446 (1967). 34
Table 50. Vibrational frequencies of nonplanar tetra-atomic (C3v) molecular ions doped in alkali halide

crystals.

These ions have four modes t'i(A 1 ), */2(Ai), v3(E) and i/4(E) which are both Raman and infrared active. The accuracy, when given by

the authors, is quoted. In other cases the accuracy is estimated to be ±1 cm-1

, except in the cases marked with an asterisk where no

idea of accuracy could be obtained. The values have been rounded off to nearest wavenumber unless the accuracy is equal to or better than ±0.5 cm-1

. ClOf, IOf and SeO|- ions go substitutionally into the lattice at the anion site such that the 3-fold axis of the ion coincides with (111) direction [1-3] in FCC alkali halides. The free ion frequencies are:

i/i = 930, = 610, i'3 = 982

i/i = 754, 1^ = 373, = 774

i/i = 807, i/2 = 432, i/3 = 737

and i/4 = 479 cm-1 for CIO3

" and 1/4 = 355, 330 cm~

for IO3

" and 1/4 = 374 cm-1 for SeO§_

.

Frequency (cm *) TemperaCrystahlmpurity MAi) ^2 (Ai) ME) ME) ture K Remarks References

NaCl:C103-

35 cio3- 1027.5 IR [ 1 ] 37 cio3- — — 1017.5 — — IR [U

KCliClOf

35 cio3- 1016 IR [U

37 C103- — — 1006 — — IR [ 1 ]

KBr:C103-

35 cio3- 947.60 628.01 1004.45 493.82 176 IR [ 1 ] 37 cio3- 940.60 623.08 994.35 492.28 176 IR [ 1 ] KLCKV

35 C103- 937.60 620.88 990.36 487.12 176 IR [ 1 ] 37 C103- 930.80 615.98 980.28 485.53 176 IR [ 1 ] KLKYr

I

1603- 791.05 ±0.15 381.7 ±0.15 806.75 ± 0.15 323.7 ± 0.15 130 IR [2] I

18 03- 749.75 ±0.15 365.6 ± 0.15 767.25 ±0.15 307.15 ± 0.15 130 IR [2] KBnSeO 3 " 845.5 780 ± 1 293 a IR [3] — 763 ± 1 293 a IR [31 — — 752.5 ± 1 293 aIR [3]

I

749 ± 1 — 293 a IR [3]

a Charge compensating defect occupying the nearest neighbour positions lowers the site symmetry of the ion resulting

in the splitting of 1/3. References

[1] Krynauw. G. N., and Schutte. C. J. H., Spectrochim. Acta [3] Demyanenko. V. P., Tsyashchenko. Yu. P.. and Verlan. 21,1947(1965). E. M., Phys. Stat. Sol. 48, 737 (1971).

[2] Klee. W. E., Spectrochim. Acta 26A, 1165 (1970).

35
Table 51. Vibrational frequencies (cm~ l ) of planar tetraatomic molecular ions (D3 /,) eloped in alkali

halide crystals.

These ions have four modest (A') Raman active, v2 (A" ) infrared active and r'.-s(E') andt'4 (E') both Raman and infrared active. The accuracy, when given by the authors, is quoted. In other cases the accuracy is estimated to be ± 1 cm -1

, except in the cases marked

with an asterisk where no idea of accuracy could be obtained. The values have been rounded off to nearest wavenumber unless the accuracy is equal to or better than ±0.5 cm -1

. NO.“, CO2-

, and BO3- enter the lattice substitutionally at the anion site such that the plane of the ion is perpendicular to the (111) direction [1, 2, 6] in FCC alkali halides.

Crystal:

Impurity

Frequency (cm 1 ) Temperature

K

Remarks References

*m(A' ) MA") ME '

)

ME '

)

NaCl:NO; r 1423 ±1 77 IR [1] NaBr:N03- 1398 ± 1 77 IR [1] NaI:NOf 1391 ±1 77 IR [1] KC1:N03- 1398 ±1 77 IR [1] KBr:N03-

,4 N 16 03- 1054.8 ±0.5 841.3 ±0.5 1382.2 ±0.5 715.6 ±0.5 8 IR [2]

14 N 160 i8 0

- 1034.9 837.8 1383.2 — 8 IR

[2]

14 N 16 0 ,8 0j — 834.3 1377.2 — 8 IR

[2]

14 N 18 03- 944.4 830.6 1363.4 8 IR

[2]

,5 N16 03- 1055.1 820.0 1352.4 714.4 8 IR

[2]

,5 N 16 OfO- — 816.4 1352.3 — 8 IR

[2] 1338.7

13 N 160 18 02_ 1344.7 , 8 IR [2] 1329.3

15 N 18 03- 1329.3 8 IR [2] KI:N03- — — 1372 ±1 — 77 IR [1]

KCl:CO|- 882 1476 300 a IR [4] 1420

1391

KCl:CO|-. Ca2+ 1520 300 a IR [3] 1398

KC1:C0 2 -. Sr2+

3 1073 880 1493 300 a IR [4] 1473 1420

1380

KC1:C0.2 -. Pb 2+ 1049 864 1551 736 a IR [5] 1333 681

KBnCOf- 883 1475 300 a IR [4] 1459

1402 1380

KBr:C0.2 -, Pb 2+ 1043 863 1556 731 a IR [5] 1319 677

KI:CO|- 885 1485 300 a IR [4] 1398

1368

KBr:B03" 952 735 1247 — 300 a IR [6] 1222

KBr:H 3B03 1040 1450 300 a IR [6] 1400

a Because of the charge compensating defect in the neighbourhood of the ion the symmetry is lowered resulting in the splitting of

Vz and v 4 .

36
References

[1] Metselaar. R., and Van der Elsken. J.. Phys. Rev. 165,359(1968 [4] Jain. S. C., and Sehgal. H. K.. Unpublished work.

[2] Rolfe. J.. J. Chem. Phys. 47, 1901 (1967). [5] Morgan. H. W., and Staats. P. A., J. Appl. Phys. 33, 364 (1962).

[3] Maksimova, T. I.. Phys. Stat. Sol. 33,547 (1969). [6] Jain. S. C., and Sehgal. H. K., Unpublished work. Table 52. Vibrational frequencies ofpenta- atomic tetrahedral molecular ions ( Td ) doped in alkali halides.

These ions have four modes of which i'j(Ai) and 1^2 (E) are only Raman active, while ^(Tz) and v4 (T2 ) are both Raman and in- frared active. The accuracy, when given by the authors, is quoted. In other cases the accuracy is estimated to be ±1 cm -1

, except in the cases marked with an asterisk wdiere no idea of accuracy could be obtained. The values have been rounded off to nearest wave- number unless the accuracy is equal to or better than ±0.5 cm -1

. These tetrahedral ions enter the lattice substitutionally such that the

four bonds are directed along the (111) directions in FCC alkali halides [2. 3]. In BCC alkali halides the tetrahedral ions occupy the anion

site such that the site symmetry is reduced to Dod [1-3]. The free ion frequencies are:

Vi 3040. vo — 1680. v3

- 3145 and V4

- 1400 cm -1 for 14nht

Vi , Vo — 1646. v3 - 3137 and V4 = 1399 cm -1 for 15NH+

Vi = 2214, vo = 1215. v3 = 2346 and V4 - 1065 cm -1 for nd4- Vi = 2264. vo — 1210, v3 = 2244 and V4 = 1080 cm -1 for bh4+

Vi = 1570, v2 = 855. v3 = 1696 and V4 = 823 cm -1 for bd 4-

Vi = 769. Vo = 353, v3 — 984 and V4 524 cm -1 for nBF4- Vi = 769, vo 353, v3 — 1016 and V4 529 cm -1 for 10 BF4-

V\ 928. Vo - 459, v3 = 1119 and V4

- 625 cm -1 for CIO4-

Vi — 845. vo = 355, v3 = 910 and V4 = 395 cm -1 for MnOiVi = 983. vo = 450. v3 = 1105 and V4 = 611 cm -1 for SOf

Vi 833. vo = 335. v3 = 875 and V4 — 432 cm -1 for SeO^ -

Vi 847, vo 348. v3 1= 884 and V4 = 368 cm^ 1 for CrO^-

Vi - 894, Vo - 381. v3 = 833 and V4 = 318 cm -1 for MoO|-

Crystal Tmpurity

Frequency (cm *) Temperature

K Remarks References

v\ (A,

VoJE) v3 (T 2 ) ^(T2 ) CsCUNH;

14 NH; 3129 1432 IR [1]

15 NH+

4 — — 3118 1426 IR [1]

CsBr:NH; 3132 1422 IR [1] CsI:NH4+ CsC1:ND~ — — 3136 1411.5 IR [1]

14 ND; 2349 1084 IR [1]

15ND4+ — — 2331 1077.3 — IR [1]

CsBr:ND; 2350 1077.3 IR [1] CsIrND; — — 2350 1070.9 IR [1] NaCUBHr 2376 ± 3 1166 ±3 120 IR [2] NaBr:BH4- — 2284 ± 3 1123 ±3 300 IR [2] NaI:BH4- 2278 ± 3 1109 ± 3 300 IR [2] KC1:BH4- — 2321 ± 3 1142 ±3 300 IR [2] KBr:BHr — 2290 ± 3 1125 ±3 300 IR [2] KI:BH 4- — 2256 ± 3 1107 ±3 300 IR [2] CsBr:BHr — 2340 ± 3 1090 ± 3 120 IR [2] CsI:BH4- — — 2298 ± 3 1070 ± 3 120 IR [2] KC1:BD4 1696 ± 3 863 ±3 300 IR [2] KBriBDp — 1678 ± 3 856 ± 3 300 IR [2] KI:BD 4- — 1657 ± 3 842 ±3 300 IR [2] CsBr:BD4- 1748 ± 3 835 ±3 120 IR [2] CsI:BD 4- — — 1707 ±3 820 ±3 120 IR [2] NaI:BF4-

io bf4- 1120.5 ±0.5 530.0 ±0.5 300 IR [3] n BFr — — 1079 ±0.5 528.0 ± 0.5 300 IR [3] KC1:BF4-

10 BF4" 1131.0 ±0.5 538.0 ±0.5 300 IR [3] n BFr — — 1090.5 ±0.5 536.5 ±0.5 300 IR [3] 37
Table 52. Vibrational frequencies of penta-atomic tetrahedral molecular ions {To) doped in alkali

halides. — Continued

Frequency (cm ') Temperature

Crystal :Impurity K Remarks References

i'i(Ai) ME) MTi) MT2 ) KBr:BF4-

,o bf4- 1124.0 ± 0.5 532.5 ±0.5 300 IR [3] "bf4- — — 1084.0 ±0.5 531.0 ±0.5 300 IR [3]

KI:BF4-

io bf4- 1116.5 ±0.5 528.0 ±0.5 300 IR [3] "BFr — — 1076.5 ±0.5 526.5 ±0.5 300 IR [3] CsBnBFr

,o bf4- 1120 ± 1 535 ± 1 300 IR [3] "bf4- — — 1080 ± 1 533 ± 1 300 IR [3]

CsI:BF4-

,o bf4- 1109 ± 1 529 ± 1 300 IR [3] "bf4- — — 1070 ± 1 527 ± 1 300 IR [3]

KC1:C104- — — 1133.7 642.6 176 IR [4] KBr:C104-

35 C104- 1122.60 636.18 176 IR [4,5]

37 cio4- — — 1109.40 633.18 176 IR [5]

KI:C10 4- 1111.00 631.78 176 IR [4,5] RbBr:C10 4- 1118.35 634.78 176 IR [4] RbI:C10 4- — — 1100.10 631.36 176 IR [4]

KBr:MnO_r 840 923 ± 1 300 IR, R [6] KI:Mn0 4- 840 913 ± 1 300 IR, R [6] RbBnMnOr — — 923.5 404.5 77 IR [7] KChSOr, B 1172 300 a IR [8] 1119

1113

KC1:S042 -, Ca2+ 982 1186 651 300 b IR [8, 9, 10] 1157 629

1090 616

KChSO*", Sr2 + 1184 300 b IR [10] 1152

1089

KCl:SOJ-, Ba2+ 979 1186 640 300 b IR [9, 10] 1147 628

1083 619

KC1:S02 "< Zn 2 + 1185 300 b IR [10] 1156 1090

KChSOJ", Cd2 + 1185 300 b IR [10] 1156

1090 KCl:S0 2 -.Pb 2 - 969 1197 300 b IR [9, 10] 1150

1048 38
Table 52. Vibrational frequencies of penta-atomic tetrahedral molecular ions ( T

) doped in alkali

halides. — Continued

Crystahlmpurity

Frequency {cm ‘) Temperature

K Remarks References

MA.) ME) MT2 ) MT2 ) KBr:SO|-, Ca2 +

34 SOf- 975 1172 77 b IR [9] 1135

1067

32 S02 - 977 1185 — 77 b IR [9] 1154

1082

KCl:SeOf-, M2 +

82 Se02 - 925.5 ± 1 904.5 ± 1 860.5 ± 1

120 b IR [11]

80 SeO2 - 836 — 928 ± 1 907 ± 1 862.5 ± 1 — 120 b IR [11]

78 SeO|" — — 930.5 ± 1 909.5 ± 1 865.0 ± 1 — 120 b IR [11]

77 Se024-' — — 931.5 ± 1 910.5 ± 1 866.0 ± 1 — 120 b IR [11]

76 Se02 - — — 933 ± 1 912 ± 1 867.5 ± 1 — 120 b IR [11]

KBr:Se0 2 ", M2 +

82 Se0 2 - 917.5 ± 1 ! 120 b IR [11] 897.5 ± 1 851.5 ± 1

80 SeO 2 - 828.5 — 920 ± 1 899.5 ± 1 854 ± 1 — 120 b IR [11]

78 Se02 - — — 922.5 ± 1 902.0 ± 1 856.0 ± 1 — 120 b IR [11]

77Se0 2_ — 924 ±1

903 ±1

857 ±1 — 120 b IR. [HI

76Se0 2 ~ — — 925.5 ±1

904.5 ±1

858.5 ±1 — 120 b IR. [HI

KC1 : CrO 2 - — M

913 ±1 — 300 IR [12|

KCl:Cr0 2 -,B 860 — 939 ±1

896 ±1

887 ±1 —- 300 a IR, [12]

39
Table 52. Vibrational frequencies ofpenta-atomic tetrahedral molecular ions (Tf) doped in alkali

halides. — Continued

Crystal :Impurity

Frequency {cm ') Temperature

K Remarks References

m(Ai) ME) MT*) MT,)

KC1 : CrO|~. Ca2 + 860 — 944 ±1

929 ±1

881 ±1 — 300 b IR, [13|

KBr: CrO 2 " — — 908 — 300 IR [121

KBr: CrO 2 ". B 856 — 927 ±1

894 ±1

888 ±1 — 300 a IR [12)

KBr: CrO 2 ". Mg2 + 856 — 937 ±1

925 ±1

880 ±1 — 77 h IR [141

KBr : CrO 2-

. Ca2 + 855 — 936 ±1

924 ±1

880 ±1

433 416

399

77 h IR [13. 14]

KBr : CrO 2 -. Sr 2 + 853 — 938 ±1

922 ±1

878 ±1

428

399

77 h IR [14)

KBr: CrO 2 -. Ba2+ 849 — 940 ±1

921 ±1

872 ±1

427

414

401

77 b IR [14|

KBr : CrO 2 -. Pb 2 + 837 — 941 ±1

920 ±1

843 ±1

415

391 378

77 b IR [141

KI:Cr02 - — — 907 — 300 b IR [12]

KI :Cr0 2 -, B 855 — 926 ±1

891 ±1

884 ±1 — 300 a IR [121

KI :Cr0 2 -, Ca2 + 855 — 928 ±1

920 ±1

875 ±1 — 300 b IR [121

KBr : MnO2- 830 — 860 ±1 — 300 IR. R [61 KBr:Mn0 2 -, B 830 — 870 ±1

842 ±1

836 ±1 — 300 a IR [6]

KBr : MnO 2-

. Ca2 +

4 830 — 890 ±1

880 ±1

846 + 1 — 300 MR [61

KBr :Mo0 2 - 898 855 ±1 — 300 IR. R [151

KBr:Mo0 2 -, B 898 — 876+1

844 ±1

834 ±1 — 300 MR [15J

40
Table 52. Vibrational frequencies ofpenta-atomic tetrahedral molecular ions (Td) doped in alkali

halides. — Continued

Crystahlmpurity

Frequency (cm -1

) Temperature

K Remarks References

^i(Aj) r 2 (E) ^)T2 ) UJ4(T2 ) KCLBeF2 " — — 837.4 ±1 — 300 b IR [16]

KC1 : BeF2-

. Mg2+ —

— 910. 4± 1 870.4 ±1

770.0 ±1 —

300 b IR [16]

KC1 : BeF2-. Ca2+ —

— 909.0 ±1

870.3 ±1

770.2 ±1 —4* 300 b IR [16]

KCl:BeF2 -.Sr2 + . 909.6 ±1

862.6 ±1

768.1 ±1

300 b IR [16]

KCl:BeF2 -.Ba2 + — 910.9 ± 1 853.4 ±1

762.7 ±1 — 300 b IR [16]

KC1 : BeFf “. Zn2 + — — 909.0 ±1

869.0 ± 1 780.0 ±1 — 300 b IR [16]

KC1 : BeF2 -. Cd2 ^ 910 + 1

768 ±1 — 300 b IR [16]

KC1 : BeF2 ". Mn2 + — —

909.8 + 1 870.0 ±1

770.0 + 1

300 b IR [16]

KClrBeF2 -. Sn 2+ — — 910.1 + 1 870.0 + 1 770.0 + 1 ^

300 b IR [16]

KC1 : BeF2 ”, Pb 2+ --- 909.8 + 1 868.0 + 1 757.6 + 1 — 300 b IR [16]

a Here the charge compensation is by an anion vacancy in one of the twelve nearest neighbour anion sites, reducing the symmetry

from Td to Cs resulting in the splitting of v$ (T2 ) into V3 (A' ) + v3 (A' ) + v3 (A" ) . Here v3 (A" ) < v% (A' )

. 0 denotes anion vacancy.

b Here charge compensation is by a divalent cation in one of the six nearest neighbour cation sites, reducing the symmetry of the ion

to C2v resulting in the splitting of 1^3 (To) into v3 (Aj) + 1^3 (61 ) -h v3 (B2 ). Here ^(Ba) > v3 (

x ) > ^(Bi). M2+ denotes unknown divalent cation

impurity.

References

[1J Price. W. C.. Sherman. W. F.. and Wilkinson. G. R.. Proc. Roy. Soc. A255, 5 (1960).

[2J Coker. E. H.. and Hofer. D. E.. J. Chem. Phys. 48. 2713

(1968).

[3] Bonadeo. H.. and Silberman. E.. J. Mol. Spect. 32, 214

(1969).

[4] Krynauw. G. N.. and Schutte. C. J. H.. Z. Phys. Chem. 55,

134 (1967).

[5] Krynauw. G. N.. and Schutte. C. J. H.. Spectrochim. Acta 21, 1947 (1965).

[6 ] Jain. S. C., Agarwal. S. K., and Singh. Risal (To be Published (1973).

[*] Manzelli. P.. and Toddei. G.. J. Chem. Phvs. 51, 1484

(1969).

[8

]

Maksimova. T. I.. Phys. Stat. Sol. 33, 547 (1969).

[9]

Decius. J. C.. Coker. E. H.. and Brenna. G. L.. Spectrochim. Acta 19, 1281 (1963).

[10] Mirlin. D. N., and Reshina. I. I.. Sov. Phys.-Solid State 10,

895 (1968).

[11] Demyanenko, V. P., Tsyashchenko, Yu. P., and Verlan,

E. M., Phys. Stat. Sol. 48, 737 (1971).

[12] Jain. S. C.. Warrier. A. V. R., and Agarwal. S. K.. Chem.

Phys. Letters 14, 211 (1972).

[13] Demianenko. V. P.. Tsyashchenko. Yu. P., and Verlan.

E. M.. Sov. Phys.-Solid State 12,417 (1970).

[14] Miller. P. J.. Cessac. G. L.. and Khanna. R. K.. Spectrochim. Acta (1971).

[15] Jain. S. C.. Agarwal. S. K.. and Singh. Risal. (Private

communication).

[16] Crzybowski. J., Khanna. R. K.. and Verble. J. L., Spectro- chim. Acta (1971). 41
Table 53. Vibrational frequencies of octahedral complexes doped in alkali halide crystals.

The Vx(A ig) and v:j(E s) stretching modes are only Raman active and the stretching mode v6(Ti H)is only infrared active. The accuracy, when given by the authors, is quoted. In other cases the accuracy is estimated to be ± 1 cm -1

, except in the cases marked with an aster- isk where no idea of accuracy could be obtained. The values have been rounded off to nearest wavenumber unless the accuracy is equal

to or better than ±0.5 cm -1. Co(CN)g _ and Fe(CN)g - (n — 3, 4, 5) ions enters the lattice substitutionally such that the metal ion occupies

the cation site and the six CN - ions occupying the six nearest neighbour anion sites in FCC alkali halides.

Crystal : Impurity

Frequency (cm 1 ) Temperature

K

Remarks References

MAlg) ":i(Ey) ^b(T i«)

NaCl :Co( 12CN)6

3 - 2142 ±1

2137 ±1

2130 ±1

2124 ±1

2121 ±1

300 a IR [1]

NaCl :Co( 13CN)3 - — — 2094 ± 1 2089 ± 1 2085 ± 1 2078 ± 1

300 a IR [1]

KC1 : Co( I2 CN)3- 2128 ±1

2126 ±1

2118 ± 1 2111 ±1

2109 ±1

300 a IR [1]

KC1 : Co( ,3 CN)3_ — — 2085 ± 1 2076 ± 1

300 a IR [1]

NaCl : Co(CN)g _ — 2094 ± 1 2086 ± 1 2081 ±1

2076 ± 1

300 ab IR [1]

KC1 :Co(CN)«- — 2085 ± 1 2076 ± 1 2067 ± 1 2063 ± 1

300 ab IR [1]

NaCl :Co(CN)b?- — — 1976 ±1 300 b IR [1]

KC1 : Co(CN)3- — — 1959 ± 1 300 b IR [1]

NaCl :Fe(CN)3 - 2131 2127 2121 ± 1 2115 ± 1 2110 ± 1

300 a IR [2]

KC1 : Fe(CN)3- 2126 2121 2109 ±1

2103 ±1

2099 ± 1

300 a IR [2]

NaCl:Fe(CN)g~ — — 2073 ± 1 2064 ±1

2050 ± 1 2047 ±1

300 a IR [2

KCl:Fe(CN)4- 2059 ± 1 2048 ±1

2032 ± 1 2028 ± 1

300 a IR [21

42
Table 53. Vibrational frequencies of octahedral complexes doped in alkali halide crystals— Continued

Frequency (cm-1

; Crystal : Impurity Temperature Remarks References

iq(Ai<,) VZ (Eg) I'sCTm) K

NaCl:Fe(CN)g~ — — 1967 ±1 300 b IR [2]

KCl:Fe(CN)*- — — 1947 ±1 300 b IR [2]

a Since there are charge compensating defects in the neighbourhood of the ions, the symmetry of the complex is lowered resultin

in the splitting of I'efTm) mode giving rise to more than one band.

b These species are produced by X-irradiating the NaCl and KC1 crystals containing Co(CN)j?~ and Fe(CN)j!- ions. References

[1] Jain. S. C., Warrier. A. V. R., and Sehgal. H. K., J. Phys. C. 5, 1511 (1972).[2] Jain. S. C., Warrier. A. V. R.. and Sehgal. H. K., J. Phys. C

6, 193 (1973).

PART III.

External Vibrational Frequencies of Impurity Centers

Doped in Alkali Halide Crystals

45

Table 54a. Frequencies of external modes {in cm'1 ) due to U-centers in alkali halides

Center LiF NaF NaCl NaBr Nal KC1 KBr KI RbCl RbBr CsCl CsBr Csl

U(H-) d 1024 d 859.5 b 563 b 498 d 426.8 d 502 d 444 b 446 d 476 d 426 d 424 d 365.5 d 283

U(D-) d 746 d 615 b 408 b 361 d 318.5 b 360 d 318 — b 340 — d 302 d 263 d 219

Ui(H) d 794 d 718

U,(D) d 567.1 d 518

H“ Na+ d 531

d 490

d 443

H- K+ — — d 686 d 493 d 442 — — —

— — d 514 d 468 d 387 — — —

d 432

H--Rb+ d 550 d 489

d 511 d 453

d 483 d 427

H- — Cs + b 617.5

b 526

b 455.5

H-F- b 519

b 493

H-Br- d 525

d 494

H--I- b 569

b 513

b 483

Assignment References

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

Localized mode

[1. 2. 3. 4, 5]

[1. 2. 3. 4, 5]

[6. 7]

[6.7]

[ 8]

[ 8]

[8]

[8. 9]

[8.9]

[8.9]

[8]

[8]

[8]

[9]

[9]

[9]

[9]

[9]

[ 8 ]

[ 8]

[9]

[9]

[9]

a Room temperature. b Liquid air/nitrogen temperature. c Liquid helium temperature. d Temperature between 4.2 and 77 K. 47
References

[lj Dotsch. H.. Phys. Stat. Sol. 31,649 (1969).

[2] Barth. W.. and Fritz. B.. Phys. Stat. Sol. 19, 515 (1967).

[3] Bauerle. D., and Fritz. B.. Phys. Stat. Sol. 24, 207 (1967).

[4] Fritz. B., Gross. U., and Bauerle. D.. Phys. Stat. Sol. 11,231

(1965).

[5| Dotsch. H.. and Mitra. S. S., Phys. Rev. 178, 1492 (1969).

[6] Durr. U., and Bauerle. D., Z. Physik 233, 94 (1970).

[7] Bauerle. D., and Fritz. B., Phys. Stat. Sol. 29,639 (1968).

[8] Barth. W., and Fritz. B., Phys. Stat. Sol. 19, 515 (1967).

[9] Mirlin. D. N., and Reshina. I. I., Sov. Phys. -Solid State 8, 116 (1966).

Table 54b. Frequencies of external modes (in cm ! ) due to point impurities in alkali halides

Center NaCl NaBr Nal KC1 KBr KI RbCl RbBr Assignment References

7Li+ d 154 Lattice mode around impurity [1]

d 141 Lattice mode around impurity [1]

d 114 Lattice mode around impurity [1]

c 43.7 — — c 42.1 c 16.07 — — — Resonant mode [1, 2, 3, 4]

6 Li+ c 45.3 — — c 39.5 c 17.71 — — — Resonant mode [1, 2, 3, 4] Na+ — — — — — c 63 — — Resonant mode [5]

K* d 143 Lattice mode around impurity UJ

d 122 Lattice mode around impurity [1]

d 87 Lattice mode around impurity [1]

Cs+ — — — — — c 83.5 — — Gap mode [5]

65Cu" c 48 Alg, T>g [6]

c 40 Eg [6]

c 23.57 Resonant mode [3]

Ag* 187.5 A]g, Eg, Tag [8] 183.7 Alg, Eg [8] 183 Eg [8] 179.2 Alg [8] 178.5 Tag [8] 164.7 Alg [8] 163.8 Tag [8] 159 Eg [8] 156 Tag [8] 155 T, u [1,8] 143 Alg [8] 142.5 Tag [8] 142 Eg [8] 131 Ti« [L8]

130.8 Tag [8]

d 122.4 Alg [8]

d 121.5 Tag [8] 120.5 Tig [1,8]

d 119.7 Eg [8]

d 113 Tag [8]

d 111.5 Eg [8]

d 104.8 A Ig, Tag [8]

d 103.5 Eg [8]

d 99.5 Eg [8]

d 59.4 Eg [8]

c 36.1 Resonant mode [1, 2, 7, 8]

c 26.4 Resonant mode [1, 2, 7, 8]

d 53 48 36.7 c 38.6 c 33.5 c 17.5 c 21.4 — Resonant mode [1, 2, 7, 8]

48
Table 54b. Frequencies of external modes (in cm *) due to point impurities in alkali halides— Continued

Center NaCl NaBr Nal KC1 KBr KI RbCl RbBr Assignment References

Mg2+ 120 • [9] Ca2+ 110 ’’ [9] Tl + a 138 E, [10]

a 135 3 123 3 113 —L-^— E, [10]

a 113 3 109 E, [10]

a 110 ' T, [10] —

3 80 3 82 _ Ei/, A/,/ [10]

3 71 __5 | E„ [10]

==.^_. 3 70 T2.v [10]

. _ 3 67 ^4: Tin [10] _ __

3 62 T2 ,/ [10] — _ _!/ 3 60 | WiWWI E, [10]

| _ f

3 51 E, [10] — — i ?— 3 50 — — t2„ [10]

F- d 144 78 Gap mode [2]

d 112 ;

1 E 70 E Gap mode [2]

d 59.5 — [11 CP — — — — 77 — — Gap mode [2]

Br- d 140 [1]

d 117 • • [1]

d 85 [1] — — 1 j 73.8 jJi;*

| Gap mode [2]

I- d 140 [1]

d 120 — — [1]

d 71 1 [1]

3 Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K. References

[1] Macdonald, H. F., Klein, M. V., and Martin, T. P., Phys. Rev. 177, 1292 (1969).

[2] Genzel, L., Optical Properties of Solids, Ed. S. Nudelman

and S. S. Mitra, Plenum Press (1969) pp. 453--487.

[3] Kirby, R. D., Nolt, I. G., Alexander, R. W., and Sievers,

A. J., Phys. Rev. 168, 1057 (1968).

[4] Kirby, R. D., Hughes, A. E., and Sievers, A. J., Phys. Rev. 2B, 481 (1970).

[5] Sievers, A. J., Localized Excitations in Solids, Ed. R. F. Wallis, Plenum Press (1969) pp. 27-45.

[6] Ganguly, B. N., Kirby, R. D., Klein, M. V., and Montgomery,

G. P., Jr., Phys. Rev. Letters 28 , 307 (1972).

[7] Sievers, A. J., Phys. Rev. Letters 13, 310 (1964).

[8] Montgomery, G. P., Jr., Klein, M. V., Ganguly, B. N., and

Wood, R. F., Preprint (1972).

[9] Weber, R., and Siebert, F., Z. Physik 213, 273 (1968).

[10]

Harley, R. T., Page, J. B., Jr. and Walker, C. T., Phys. Rev. Letters 23, 922 (1969).

49
Table 55a. Frequencies of external modes (in cm x ) due to molecular impurities in alkali halides

Center NaCl NaBr Nal KC1 KBr KI RbCl RbBr Rbl Assignment References

NCO- b 86 b 165 b 172 b 194 h 183.6 b 172.5 b 109 b 153.6 b 114.5 [11

b 136 b 105 b 147 b 167.5 b 152.5 b 101 b 141 b 101 [11

b 127 b 91 b 115 b 157 b 133 b 87 b 31 b 87 [11

b 123 b 35 b 52 b 122 "119 ”36 h 62 [11

b 117 b 105 b 82.2 . b 57 [1]

b 106 b 99.7 b 77.8 b 24 [1]

b 90 b 97.4 b 59 [11

b 84 b 31 [1] b 79 [1] — — — — b 41 — — — — — [1] Na- b 124 b 105 b 178 b 145 b 155 b 126 [11 — — — — b 97 b 80 — — — — [1] bo2- b 169 b 139 [1] — — — — b 102 b 88 — — — — [11 NOr d 89.2 Gap mode [2]

d 88 Gap mode [2]

d 79.4 Gap mode [2]

d 78 Gap mode [2]

d 72.8 Gap mode [2] — — — — — d 71.1 — — — Gap mode [2]

NO:7 b 175 b 182 [1]

b 143 b 111 [1] b 103 b 89 [1] — — — — b 93 b 74 — — — — [1] CN- b 189 b 197 b 165 [1]

b 147 b 154 b 126 [1]

b 132 b 122 b 93 [1]

b 114 [1]

b 109 fU

c 83 Gap mode [3,4]

c 68 Translational mode [3]

b 45 b 35 b 26 c 43 [1,3] — — — c 12 c 12 c 11 d 19 — — Librational mode [1,3,5]

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K. References

[1] Cundill, M. A., and Sherman, W. F., Phys. Rev. Letters 16,

570 (1966).

[2] Renk, K. F., Phys. Letters 14, 281 (1965).

[3] Seward, W. D., and Narayanamurti, V., Phys. Rev. 148,463

(1966).

[4] Lytle, C. D., and Sievers, A. J., Bull. Am. Phys. Soc. 10,616

( 1965). [5] Narayanamurti, V., and Pohl, R. O., Rev. Mod. Phys. 42,

201 (1970).

50
Table 55b. Frequencies of external modes (in cm-1

) due to 0H~ and 0D~ in alkali halides

Center NaCl Nal KC1 KBr KI RbCl CsBr Assignment References

OH- c 390 427 c 297.5 c 312.7 c 284 c 272 289 Librational mode [L 2, 3]

c 86.9 Gap mode [4]

c 86.2 Gap mode [4]

c 86 c 77 [4, 5]

c 68 c 69.5 [4,5]

c 12.2 c 32 c 37.5 c 30 Non-Devonshire line [4, 6, 7]

c 22 — [7]

c 15.6 — [7]

c 9.3 — [7]

c 2 — — [7] OD- c 232 c 236.3 c 215 Librational mode [1,2]

c 86 [5]

c 68 [5] — — — c 35 — — — Non-Devonshire line [5]

a Room temperature.

b Liquid air/nitrogen temperature.

c Liquid helium temperature.

d Temperature between 4.2 and 77 K. References

[1] Klein, M. V., Wedding, B., and Levine, M. A., Phys. Rev. 180,902(1969).

[2] Harrison, J. P., and Luty, F., Int. Conf., Color Centers in Alkali Halides, Rome (1968).

[3] Wedding, B., and Klein, M. V., Phys. Rev. 177, 1274 (1969).

[4] Renk, K. F., Phys. Letters 20, 137 (1966).

[5] Bosomworth, D. R., Solid State Comm. 5, 681 (1967).

[6] Chau, C. K., Klein, M. V., and Wedding, B., Phys. Rev.

Letters 17, 371 (1967).

[7] Kirby, R. D., Hughes, A. E., and Sievers, A. J., Phys. Rev. B2, 481 (1970).

51
FORM NBS-114A (1-71) u.s. DEPT, of COMM. 1. PUBLICATION OR REPORT NO. 2. Gov t Accession

BIBLIOGRAPHIC DATA No* sheet nbs =NSR DS =5 z

3. Recipient s Accession No.

4. TITLE AND SUBTITLE

Electronic Absorption and Internal and External Vibrational

Data of Atomic and Molecular Ions Doped in Alkali Halide

Crystals

5. Publication Date July 1974

6. Performing Organization Code

7. AUTHOR(S)

S,C. .TR-in, A.V.R. Warrier , and S.K. Agarwal

8. Performing Organization

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

10. Project/Task/Work Unit No.

11. Contract/Grant No.

12. Sponsoring Organization Name and Address

Same as No, 9.

13. Type of Report & Period

Covered

Final

14. Sponsoring Agency Code

15. SUPPLEMENTARY NOTES

Library of Congress Catalog Card Number: 74-600010

16. ABSTRACT (A 200-word or less factual summary of most significant information. If document includes a significant

bibliography or literature survey, mention it here.)

Spectral data for more than 70 atomic and molecular ions doped in alkali halide

crystals are tabulated. The tables include electronic absorption data, listings

of internal vibrational frequencies of doped complex ions, and tabulations of the

frequencies of external modes. The data that appear in the tables were selected

on the basis of the consistency among different authors, the types of instruments,

and the temperature of measurement. In addition to the data, the tables include

the spectroscopic assignments given by the authors in the references cited.

17. KEY WORDS (Alphabetical order, separated by semicolons)

Atomic ions; doped alkali halide crystals; external vibrational modes; internal

vibrational modes; molecular ions.

1 8. AVAILABILITY STATEMENT 19. SECURITY CLASS 21 (THIS REPORT)

• NO. OF PAGES

|LXj UNLIMITED.

I I FOR OFFICIAL DISTRIBUTION. DO NOT RELEASE

TO NTIS.

59

UNCL ASSIFIED

20. SECURITY CLASS

(THIS PAGE)

22. Price

95 cents UNCLASSIFIED

USCOMM-DC 66244-P71
Announcement of New Publications in

National Standard Reference Data Series

Superintendent of Documents,

Government Printing Office,

Washington, D.C. 20402

Dear Sir:

Please add my name to the announcement list of new publications to be issued

in the series: National Standard Reference Data Series — National Bureau of

Standards.

Name

Company

Address

City State Zip Code

(Notification key N-337)

U. S. GOVERNMENT PRINTING OFFICE : 1974 O - 532-811

NBS TECHNICAL PUBLICATIONS

PERIODICALS JOURNAL OF RESEARCH reports National

Bureau of Standards research and development in physics, mathematics, and chemistry. Comprehensive

scientific papers give complete details of the work,

including laboratory data, experimental procedures,

and theoretical and mathematical analyses. Illustrated

with photographs, drawings, and charts. Includes

listings of other NBS papers as issued.

Published in two sections, available separately:

• Physics and Chemistry (Section A)

Papers of interest primarily to scientists working in

these fields. This section covers a broad range of

physical and chemical research, with major emphasis on standards of physical measurement, fundamental

constants, and properties of matter. Issued six times a year. Annual subscription: Domestic, $17.00; Foreign, $21.25.

• Mathematical Sciences (Section B)

Studies and compilations designed mainly for the

mathematician and theoretical physicist. Topics in mathematical statistics, theory of experiment design,

numerical analysis, theoretical physics and chemistry,

logical design and programming of computers and

computer systems. Short numerical tables. Issued quarterly. Annual subscription: Domestic, $9.00; Foreign,

$11.25.

DIMENSIONS, NBS

The best single source of information concerning the

Bureau’s measurement, research, developmental, co- operative, and publication activities, this monthly

publication is designed for the layman and also for

the industry-oriented individual whose daily work

involves intimate contact with science and technology —for engineers, chemists, physicists, research managers, product-development managers, and company

executives. Annual subscription: Domestic, $6.50; Foreign, $8.25.

NONPERIODICALS Applied Mathematics Series. Mathematical tables,

manuals, and studies.

Building Science Series. Research results, test methods, and performance criteria of building materials, components, systems, and structures. Handbooks. Recommended codes of engineering

and industrial practice (including safety codes) developed in cooperation with interested industries,

professional organizations, and regulatory bodies.

Special Publications. Proceedings of NBS conferences, bibliographies, annual reports, wall charts,

pamphlets, etc. Monographs. Major contributions to the technical

literature on various subjects related to the Bureau’s

scientific and technical activities. National Standard Reference Data Series.

NSRDS provides quantitative data on the physical

and chemical properties of materials, compiled from

the world’s literature and critically evaluated.

Product Standards. Provide requirements for sizes,

types, quality, and methods for testing various industrial products. , These standards are developed co- operatively with interested Government and industry

groups and provide the basis for common understanding of product characteristics for both buyers and

sellers. Their use is voluntary.

Technical Notes. This series consists of communications and reports (covering both other-agency and

NBS-sponsored work) of limited or transitory interest. Federal Information Processing Standards

Publications. This series is the official publication

within the Federal Government for information on

standards adopted and promulgated under the Public

Law 89—306, and Bureau of the Budget Circular A—86

entitled. Standardization of Data Elements and Codes

in Data Systems.

Consumer Information Series. Practical information, based on NBS research and experience, covering areas of interest to the consumer. Easily understandable language and illustrations provide useful

background knowledge for shopping in today’s technological marketplace.

BIBLIOGRAPHIC SUBSCRIPTION SERVICES

The following current-awareness and literature-survey bibliographies are issued periodically by the

Bureau

Cryogenic Data Center Current Awareness Service (Publications and Reports of Interest in Cryogenics).

A literature survey issued weekly. Annual subscription : Domestic. $20.00; foreign, $25.00.

Liquefied Natural Gas. A literature survey issued quarterly. Annual subscription: $20.00.

Superconducting Devices and Materials. A literature survey issued quarterly. Annual subscription: $20.00.

Send subscription orders and remittances for the preceding bibliographic services to the U.S. Department

of Commerce, National Technical Information Service, Springfield, Va. 22151. Electromagnetic Metrology Current Awareness Service (Abstracts of Selected Articles on Measurement

Techniques and Standards of Electromagnetic Quantities from D-C to Millimeter-Wave Frequencies). Issued monthly. Annual subscription: $100.00 (Special rates for multi-subscriptions) Send subscription order and

remittance to the Electromagnetic Metrology Information Center, Electromagnetics Division, National Bureau

of Standards, Boulder, Colo. 80302. Order NBS publications (except Bibliographic Subscription Services;

from: Superintendent of Documents, Government Printing Office, Washington, D.C. 20402.