TEXT BOGK MOLECULAR SPECTRA and MOLECULAR STRUCTURE I. SPEcTRA OF DIATOMIC MOLECULES BY GERHARD HERZBERG, F.R.S. National Research Council of Canada With the co-operation, in the first edition, of J. W. T. SPINKS, F.R.S.C. SECOND EDITION, EIGHTH PRINTING D. VAN NOSTRAND COMPANY, INC. PRINCETON, NEW JERSEY TORONTO LONDON NEW YORKD. VAN NOSTRAND COMPANY, INC. 120 Alexander St., Princeton, New Jersey (Principal office) 24 West 40 Street, New York 18, New York D. Vaw Nostrano Company, L: 358, Kensington High Street, London, W.14, England D. Van Nosrranp Company (Canada), Lro. 25 Hollinger Road, Toronto 16, Canada Copyright © 1950 py D, VAN NOSTRAND COMPANY, Ine. Published simultancously in Canada by D. Van Nosrranp Company (Canada), Len, First Edition Copyright 1939 by Prentice-Hall, Ine, No reproduction in any form of this book, in whole or in part (except for brief quotation in critical articles or reviews), may be made without writlen authorization from the publishers, First Published May 1950 Reprinted February 1961, November 1953 November 1955, February 1957, August 1969, December 1961, February 1963 PRINTED IN THE UNITED STATES OF AMERICADedicated to the Memory oi Watrer Cares Murray First President of the University of SaskatchewanPREFACE Eleven years ago I published a volume entitled Molecular Spectra and Molecular Structure I. Diatomic Molecules which was followed in 1945 by a second volume /nfrared and Raman Spectra of Polyatomic Molecules. The first volume has been out of print for a number of years but the demand for it seemed to justify a new edition. Although the book has been completely revised and brought up to date, its gencral plan has remained substantially unchanged. Concerning this plan it seems therefore appropriate to quote from the preface of the first edition: “1 have endeavored to give a presentation which is readable by the beginner in the field and also will be useful to those who do or want to do research work in this field. In order to assist the former, I have frequently made use of small type for those sections that are not necessary for an understanding of the fundamentals. For the benefit of those working in the field, numerous references to original papers have been included. “A satisfactory presentation of molecular spectra and molecular structure is nowadays not possible without treating thoroughly, apart from the empirical results, the theoretical background also. Therefore I have included as much of the theory of molecular spectra as is possible without going into the more difficult, mathematical details. A large number of diagrams, graphical repre- sentations of eigenfunctions and potential curves, as well as energy level dia- grams, serve to illustrate and to explain the theory. On the other hand, I have added numerous carefully selected spectrograms of bands and band systems (some of which have been taken specially for this purpose) in order to give an accurate idea of the experimental material that forms the basis of the developments. “While of course most of the material presented is not new, it seems that the actual procedure followed in analyzing a band spectrum has not previously been giver as specifically in a book of this kind. The same holds for the ap- plications of band spectra to other parts of physics, to chemistry, and to astro- physics given in the last chapter. I hope that both these features will be found useful.” In the cleven years since the publication of the first edition the subject Spectra of Diatomic Molecules has developed vigorously even though not as rapidly as in the preceding two decades. Most of the progress made has been consolidation and slow evolution rather than revolution. Exceptions to this statement are the amazing advances made by applying the new tools of molecular beams and microwaves to diatomic molecular problems. vvi PREFACE Naturally I have incorporated these advances of recent years in the present new edition. In addition I have amplified and extended the theoretical sections of the book in response to suggestions of several critics of the first edition, I have added new sections on Radiofrequency (Microwave) Spectra (in Chapter ~ ID), Hyperfine Structure (in Chapter V) and Intensities of Electronic Transitions (in Chapter VI) and I have completely rewritten many other sections. In order to improve the presentation and to bring it up to date I have scrutinized every sentence and every illustration. Thus the reader familiar with the old edition will find much revision and modification in detail. Twenty-six new illustrations have been added of which some, like Fig. 57 showing the symmetric top eigenfunctions, have not previously been given in the literature of the subject. The table of molecular constants of the first edition included only the ground states of all diatomic molecules then known. Following the suggestions of many spectroscopists and in view of the fact that the available tables that include the excited states are now out-dated I decided to undertake the rather arduous task of preparing a comprehensive table of all known states of all known diatomic molecules. ‘This table is presented in the Appendix (Table 39) and now covers 80 pages. I have made every effort to make this table as compre- hensive and consistent as possible (see the introduction to it, p. 501). The literature up to September 1949 and in some cases up to February 1950 has been included in the table. The manuscript of the text matter of the book was completed in August 1948, and only in a few cases was it possible to include later developments in the proofs. As in the first edition the detailed subject index at the end of the book includes all the more important symbols and quantum numbers used as well as all the molecules treated. Part II of the bibliography of the first edition was taken over and a new Part IIT added giving all the references to work published since then or to earlier work not used in the first edition. G. Herzpera Orrawa, Ont. February, 1950ACKNOWLEDGMENTS It gives me great pleasure to acknowledge the help and cooperation I have received from many persons during the preparation of this book. My sincere thanks are due to Dean J. W. ‘I. Spinks who translated the original version into English and to Professor R. N. II. Haslam who contributed many stylistic improvements to the first edition. I am very grateful to Professor R. S. Mulliken for suggesting several important improvements. I should like to express my thanks to Professor 8. Chandrasekhar for making many valuable suggestions and for reading parts of the manuscript and the proofs. Many colleagues helped by supplying advance information on molecular constants for Table 39. Of these I should like to mention particularly Dr. R. F. Barrow (Oxford) and Professor FE. Miescher (Basel). The help given by Dr. J. G. Phillips (Williams Bay) and Dr. D. Andrychuk (Ottawa) in especially taking a number of new spectrograms for the present edition is much appreciated. Thanks are also due to the following spectroscopists for supplying the originals of various spectrograms of the new and the old edition: Dr. E. Bengtsson-Knave (Stockholm), Professor R. T. Birge (Berkeley), Dr. B. A. Brice (Philadelphia), Professor W. G. Brown (Chicago), Professor F. A. Jenkins (Berkeley), Professor R. Mecke (Freiburg), Professor R. $. Mulliken (Chicago), Dr. R. W. B. Pearse (London), Professor F. Rasctti (Baltimore), the late Lord Rayleigh, and Pro- fessor I. W. Wood (Baltimore). Finally I am greatly indebted to my wife who prepared all the illustrations of the first edition and made numerous sugges- tions for improving the text of the new edition. G. HrzBEereCONTENTS INTRODUCTION. .... . General remarks, 1—Physical constants, 2--Units and conversion factors, 3 CHAPTER I: RESUME OF THE ELEMENTS OF ATOMIC STRUC- TURE. 1, Bor Tarory. Stationary energy states, 5 spectra, 8 Radiation, 6 -Terms, 8- -Continuous 2. Wave Mucuantes (QUANTUM MECHANICS) .0.....2.ccccccee eves Fundamental equations, 9—Physteal interpretation of the ¥ func- tion, 12—Orthogonality and normalization of eigenfunctions, 13-— Perturbation theory, 13. -Heixenberg’s uncertainty principle, 15— Momentum and angular momentum, 15—Space quantization, 17— Electron spin, 18 -Emission and absorption of radiation, 18 3, Aros wirn Severar Buacreons; Vector Move Quantum numbers of the individual electrons, 22—The Pauli principle, 22—Quantum theoretical addition of angular momentum vectors, 24--Quantum numbers and angular momenta of the whole atom; term symbols, 26—Influence of a magnetic or electric field, 28—Selection rules, 283—Nuclear spin, 29 CHAPTER I: OBSERVED MOLECULAR SPECTRA AND THEIR REPRESENTATION BY EMPIRICAL FORMULAK................ 1. SpRcrRa IN THE Vistar: anv Unrraviounr Reaions Coarse structure, 30—Fine structure, 42 Intensity distribution, 50 2. Specrra in tue INFRARED Rx Near infrared spectra, 5 ON. . Far infrared spectra, 57 3. RADIOFREQUENCY (MICROWAVE) SPECTRA. .........000cc cece seen sees Microwave absorption, 59—Magnetie resonance spectra, 60 4, RAMAN SPECTRA. . 02.00... ccs cee ece ene e ee nee er se ene e eee rete rege Nature of the Raman effect, 61—Large Raman displacements, 61— Small Raman displacements, 63 CHAPTER III: ROTATION AND VIBRATION OF DIATOMIC MOLE- CULES; INTERPRETATION OF INFRARED AND RAMAN SPECTRA 7 ~ ay 1, INTERPRETATION OF THE PrincrraL Features or Inrrarep AND RaMaN Spxcrra BY Means or tHe Mopets or rae Riu Rorator AND OF THE Harmonic Osctuuator 22 30 53 6Lx CONTENTS (a) The Rigid Rotator... The molecule as a rigid rotator, 66—Energy levels, 67-—Bigenfunc- -tions, 69—Spectrum, 70 Ab) The Harmonic Oscillator. The molecule as a harmonic oscillator, 73—Energy levels, 75— Figenfunctions, 76—Spectrum, 79 (©) Comparison with the Observed Infrared Spectrum. (a) The Raman Spectrum of the Rigid Rotator and of the Harmonie Oseillator........ Classical theory of light scattering and of the Raman effect, 82— Quantum theory of the Raman effect, 85+Vibrational Raman spectrum, 86-7Rotational Raman spectrum, 88—General remarks, 90 2. INTERPRETATION OF THK Finer Devas or INrrarep 1 SpectRa.... (a) The Cl he molecule as an anharmonic oscillator, 90-—Classical motion, 91—Energy levels, 92—Nigenfunctions, 93—{nfrared spectrum, 94Raman spectrum, 97—Vibrational frequency and force con- stant, 97—Continuous term spectrum and dissociation, 98—Mathe- matical representation of the potential curves, 101 (b),The Nonrigid Rotator. .2........ 0000 6o cece cece cece eeeeeees zy Energy levels, 103—Spectrum, 105 (c) The Vibrating Rotator Energy levels, 106— Raman spectrum, 114 (@) The Symmetric Top.. : . ‘The diatomic molecule as a symmetric top, 115—Angular momenta, 116—Energy levels, 117—Kigenfunctions, 118—Infrared spectrum, 119—Raman spectrum, 121 (©) Thermal Distribution of Quantum Stat Vibration Spectra. - Vibration, 122—Rotation, 124 (f) Symmetry Properties of the Rotational Levels. Positive and negative rotational levels, 128—Symmetrie and anti- symmetric rotational levels for homonuclear molecules, 130—In- fluence of nuclear spin, 133—Influence of nuclear statistics, 135-— Ortho and para modifications, 139—Isotopic molecules, 141 Aig) Isotope Eitect..... ee eecccececcceceeeeeessseeeevesseeeveneees / Vibration, 141-+ Rotation, 143 Raman izonfunctions, 109—Infrared speetrum, 110— ; Intensities in Rotation- CHAPTER IV: ELEMENTARY DISCUSSION OF ELECTRONIC STATES AND ELECTRONIC TRANSITIONS. .........0000000c0ceereeeeeeee 1, Evecrnonie Eweroy ano Toran ENERGY.....000000006000000 cee Electronic energy and potential curves; stable and unstable molec- 73 81 82 90 103 106 15 121 128 141 146 146CONTENTS ular svates, 148—Resolution of the total eigenfunction, 147—Reso- lution of the total energy, 149 2, Vinrarionat SrructuRE or Euzcrronic TRANSITIONS. General formulae, 151—Examples; graphical representation, 1 Absorption, 155—-Excitation of single progressions in emission, 158-—-Sequences (diagonal groups), 159—Vibrational analysis, 161—Isotope effect, 162—Applications of the isotope effect, 165 3, Rorationan Srrucrorn oF Evecrronic BANDS....... General relations, 168—The branches of a band, 169—Band-head formation; shading (degrading) of bands, 171—-Combination re- lations and evaluation of the rotational constants for bands without Q branches, 175—Combination differences and evaluation of rota- tional constants for bands with @ branches, 183—Determination of the band origins (zero lines), 185—Determination of the number- ing in the branches of incompletely resolved bands, 180—The picking out of branches, 191—Isotope effect, 192 4, Inrensiries in Evecrronic Banps. . (a) Intensity Distribution in the Vibrational Structure Observed intensity distribution in absorption, 193—The Franck- Condon principle: absorption, 194—The Franck-Condon principle: emission (Condon parabola), 196—Wave-mechanical formulation of the Franck-Condon principle, 199—Vibrational sum rule and vibrational temperature, 203 (b) Intensity Distribution in the Rotational Structure...............+ —'¥ transitions, 204-—Other transitions, 207—Intensity alter- nation, 209--Wood’s resonance series, 210 CHAPTER V: FINER DETAILS ABOUT ELECTRONIC STATES AND ELECTRONIC TRANSITIONS 1, Crassirication oF Eumcrronic Staves; MULTIPLET STRUCTURE. ..... Orbital angular momentum, 212—Spin, 214—Total angular momen- tum of the electrons; multiplets, 214—Symmetry properties of the electronic eigenfunctions, 217 2. Covpuiva or Rotation anp Evectnontc MoTION........600000eee (a) Hund’s Coupling Cases Hund’s case (a), 219—Hund’s case (b), 221—Hund’s ease (c), 224— Hund’s case (d), 225—Hund’s case (e), 226 (b) Uncoupling Phenomena. ‘A-type doubling, 226—Transition from case (b) to case (d) (I. un- coupling), 220—Transition from case (a) to case (b) (spin uncou- pling, 231—Transition from case (b) to case (c), 237 (© Symmetry Properties of the Rotational Levels...........2-..00005 E states, 237—IT, A, .. . states, 239 151 168 204 212 212 218 219xii CONTENTS PAGE 3. Types or ELECTRONIC TRANSITIONS (a) Selection Rules General selection rules, 240--Selection rules holding for case (a) as well as case (b), 241 —Selection rules holding only in case (a), 242-— Selection rules hold:ng only in case (b), 244—Selection rules holding only in case (c), 244—Seiection rules holding only in case (d), 244— More general cases, 245 (b) Allowed Electronic Transitions. ...... Notation, 245—!5—13 transitions, 245-—?2 33— = transitions, 250—'l —'S transitions, transitions, 256—"II--S transitions, 257—?2—*I1 transitions, 264—11—*¥ transitions, 264—8S—SII transitions, 265--II—Y transitions of higher multiplicities, 266---'I—'II transitions, 266—"11—211 transitions, 268—SI1 11 transitions, 271—I—IT transitions of higher multiplicity, 272—Il—A transitions, 273— A-A transitions, 273—Band structures in Hund’s eases (c) and (d), 273—General remarks on the technique of the analysis of multiplet bands, 274 245 (e) Forbidden Electronic Transitions ..... 2.0.0... 06000. e cece eens 275 Violation of approximate selection rules, 275—Quadrupole and mag- netic dipole radiation, 277—Hnforeed dipole radiation, 280 4, PERTURBATIONS. 2.20... 6 606 c eee ete e eee e eee 280 Observed phenomena, 280—Ceneral considerations, 282—Selection rules for perturbations, 284—Rotational perturbations, 286— Vibrational perturbations, 202—Intersection of potential curves and the non-crossing rule, 295 5. Zeeman Ervect anp Stark Errect.. : General remarks on the splitting of molecular | energy levels i ina magnetic field, 298—The Zeeman splitting of | states, 299-- Zeeman effect in Hund’s case (a), 300—Zeeman effect in Hund’s case (b), 303—Other cases, 304—Polarization of resonance fluor- escence, 305— Magnetic rotation spectra, 306—Stark effect, 307 298 6. Hyrerrine Structure. Hyperfine structure without field, 308—Zeeman effect of hyperfine structure, 311 308 CHAPTER VI: BUILDING-UP PRINCIPLES, ELECTRON CONFIGURA- TIONS, AND VALENCE 1. DererMINATION oF THE TeRM MANIFOLD FROM THE STATES OF THE Separatep ATOMS. Unlike atoms, 316: Like atoms, 320 2. DererminatTion or THE TerM MANIFOLD FROM THE STATES OF THE Unrtep Atom. Unlike atoms, 322—Like atoms, 322 322CONTENTS PAGE 8. Derenmination oF THE TeRM Mantroup FRoM THE Exectron Con- FIGURATION, (a) Quantum Numbers of the Individual Electrons. Single electron in an axially symmetric electric field, 323—Several electrons, 331 (b) The Pauli Principle in the Molecule. (c) Derivation of the Term Type (Species) from the Electron Configura- tion in Russell-Saunders Coupling Terms of non-equivalent electrons, 333—Terms of equivalent elec- trons, 335—Electron configurations with equivalent and non- equivalent electrons, 336—Like atoms, 337 333 (d) Derivation of the Term Type (Species) for Other Types of Coupling. 337 (aa) coupling, 337—(2,,w) coupling, 3388—Other types of eou- pling, 338 (e) Term Manifold of the Molecule, Examples. ... General considerations, 338—H» and the hydrides, 339—Molecules with nuclei of equal charge, 344—Other molecules, 346 4. Srapiuity or Morecucar Execrronic Srates; VALENCE. (a) Homopolar Binding (Atomic Binding)... . wee ‘Treatment of the Hy molecule according to Heitler and London, 350-—Generalization of the Heitler-London theory for more com- plicated cases, 354~-Theory of bonding and antibonding electrons for equal nuclear charges, 359—Unlike nuclear charges, 367 (b) Heteropolar Binding (lonie Binding) . Tonic molecules, 373-~Transition cases, 374—Ionicity and polarity, 375 (c) Van der Waals Binding ............... 060.200 c cece eect tree eee 5. Inrensities or ELectronic TRANSITIONS. General formulae, 382—Rydberg transitions, 383—Charge-transfer spectra, 384—Other sub-Rydberg transitions, 385 CHAPTER VII: CONTINUOUS AND DIFFUSE MOLECULAR SPECTRA: DISSOCIATION AND PREDISSOCIATION.. 1, Continvous Spectra AND Bano Convercence Limits: Dissociation or Diatomic Mouecuues. (a) Absorption. . Tonization continua, 387-—Dissociation continua, 388 —Upper state continuous, 388—Lower state or both lower and upper state con- tinuous, 394 (b) Emission Upper state continuous (molecule formation in a two-body col- lision), 400---Lower state continuous, 402—Both upper and lower state continuous, 405xiv CONTENTS PAGE 2. DirFuse Mouxcunar Srecrna, Prepissociarion, AND RELATED Tortcs. 405 (a) General Discussion of Spontaneous Radiationless Decomposition Processes........ 405 ‘The Auger process, 405—Passage through potential barriers, 408 (b) Radiationless Decomposition Processes in the Molecule. 409 Diffuseness of the bands, 410—Photochemical decomposition, 411—Breaking-off of bands, 412—Different types of predissocia- tion, 413—Preionization, 414—Inverse predissociation, 414— Accidental predissociation, 415 (c) Selection Rules for Predissociation. . Kronig’s selection rules, 416—Forbidden predissociations, 419 — Preionization, 419 (4) The Franek-Condon Principle in Predissociation. .. . Case I of predissociation, 420—Case IIT (predissociation by rota~ tion); effective potential curves, 425—Influence of rotation in case I, 430 (©) Pressure Effects in Predissociation 432 Induced predissociation, 432—Suppression of breaking-off by pres- sure, 433 () Other Diffuse Molecular Spectra. . .. 435 3, DETERMINATION oF Heats ov Drssocration. 437 (a) Determination of Dissociation Limits... (1) Band convergences, 438—(2) Iixtrapolation’ to convergence limits, 438—(3) Long-wave-length limit of an absorption con- tinuum, 441—(4) Predissociation limits, 442—(5) Excitation of atomic fluorescence, 443—(6) Photodissociation, 443—-(7) Chemi- luminescence, 443 444 (b) Determination of the Dissociation Products. . . . (1) Energy differences of dissociation limits, 444—(2) Application of the Wigner-Witmer correlation rules, 445—(3) Application of the non-crossing rule, 445—(4) Observation of atomic fluorescence, 445—(5) Use of thermochemical data, 445 (C) Examples coe oscun60e eG Oz, 446—No, 449 CHAPTER VIII: EXAMPLES, RESULTS, AND APPLICATIONS....... 451 1. Eneroy Leven Dracrams; MoLecuuar CoNSTANTS.......000000000+ 451 Empirical relations, 453—Ionization potentials, 459 2. Applications T0 OrHer Fretps oF Puysics 460 Nuclear physics, 460—Paramagnetism, 462—Collision processes, 463—Nature of the liquid and the solid state, 464—Determination of high temperatures, 465—-Calculation of thermodynamic quanti- ties, 466CONTENTS xv 3, AppLications To Cuemustny Free radicals, 472-—Elementary chemical reactions in gases and chemiluminescence, 473—Photochemical primary processes, 477— Chemical equilibria, 479—Atomic heats of formation and related topics, 480 4, Appiications To ASTROPHYSICS... . ‘Absorption spectrum of the earth’s atmosphere, 482—Emission spectrum of the carth’s atmosphere, 484—Planetary atmospheres, 486—Comets, 488—Stellar atmospheres, 491-Interstellar space, 496 APPENDIX: Vinrationat anv RorationaL Constants FoR THE ELECTRONIC States ov ati Known Diaromic Motecuces (Taste 39).... 501 BIBLIOGRAPHY............0seeec eee ee cece ree eeeneee rete en eeneeeee eens 582 AUTHOR INDEX. BUBJECT INDEX........... ce ceece esse eter een e eet e ete e een nnnene eens 627INTRODUCTION General remarks. In the course of the last three decades, very consider- able progress has been made in the investigation and theoretical interpretation of molecular spectra. As a result the study of molecular spectra has become one of the most important, perhaps the most important, means for investigating molecular structure. From the spectra the various discrete energy levels of a molecule can be derived directly. From these again, we can obtain detailed information about the motion of the electrons (electronic structure) and the vibration and rotation of the nuclei in the molecule. The study of electronic motions has led to a theoretical understanding of chemical valence. From the vibrational frequencies the forces between the atoms in the molecule, as well as the heats of dissociation of molecules, can be calculated with great accuracy. From the rotational frequencies we obtain accurate information about the geometrical arrangement of the nuclei in the molecule—in particular, extremely accurate values of the internuclear distances. The knowledge of the various properties of the individual molecules so obtained allows us to understand many of the physical and chemical properties of the gases under consideration and, in fact, in many instances allows us to predict these properties—for example, the specific heat and the paramagnetic susceptibility. Also, on the basis of this knowledge, chemical equilibria can be predicted theoretically with great accuracy and chemical elementary processes can be elucidated. A further important result of the investigation of molecular spectra is that proof has been obtained of the existence of a large number of molecules which were previously unknown in chemistry or were not thought capable of free existence. Among these are CH, OH, Cz, Hep, Nag, CP, and many others. The structures of these molecules have also been determined. The investigation of the spectra of diatomic molecules is also of great significance for the physics of atomic nuclei, since certain nuclear properties influence these spectra in a characteristic manner and can therefore be deter- mined from them, and since, furthermore, in some cases rare isotopes may be detected by means of these spectra. Finally, in recent years, a new field of application of the knowledge of molecular spectra has opened up in astrophysics. Not only can the presence of various molecules on fixed stars, planets, and comets, in the upper atmosphere, and in interstellar space be detected on the basis of their spectra, but also from a more detailed analysis definite conclusions can be drawn concerning the physical conditions in these objects. This first volume deals with the spectra of diatomic molecules and the con- 12 INTRODUCTION clusions that can be drawn from them concerning the structure of these mole- cules. The spectra of polyatomic molecules will be taken up in the second and third volumes of this series. The former, already published (28),' deals with the infrared and Raman spectra; the latter will deal with the electronic spectra of polyatomic molecules. Since a thorough treatment of molecular spectra presumes a certain knowledge of atomic spectra and atomic structure, a short survey of the fundamentals of atomic theory is given in the first chapter of this volume. The experimental methods for the production and investigation of spectra will not be dealt with here. Reference should be made to Sawyer (4b), Harrison, Lord, and Loofbourow (4c), Meissner (4a), Baly (2), Brode (3), Jenkins and White (6b), and Kayser-Konen (1). The nomenclature of the various quantities concerning the molecule— energy levels, quantum numbers, and so on—was made subject to international regulation in 1930 [Mulliken (515)]. We shall use this international nomencla- lure throughout. TABLE 1. PHYSICAL CONSTANTS 2.99776 X 10'° em/see Velocity of light in vacuum ¢ Planck's constant" h 6.623; X 10°*7 erg sec Electronic charge € 4.8024 X 1071 abs. Electronic mass (rest mass) m 9.1055 X 10-* gm fg mass of the O18 atom Mm 1.65972 X 10-4 gm Number of atoms in a mol: Referred to Aston’s atomic weight seale (08 = 16) Na 6.0251 x 107% Referred to the chemical atomic weight seale Nen — | 6.0235 x 10 Boltzmann's constant k 1,38033 X 10-18 ergs/degree 7 Gas constant per mol? (chemical) R 8 “_e poe ae bea! 1 thermochemical calorie (defined)* cal 4.18400 abs, joules Physical constants. The best values of various fundamental physical constants have been the subject of much discussion. We accept here the values recently recommended by DuMond and Cohen (914) which are based on and 1 The numbers in parentheses refer to the bibliography, p. 583. 4* In an erratum received too late for inelusion in this book, DuMond and Cohen give 6.62373 X 10-*” for A. ‘The difference is smaller than the probable error. 2 "The gas constant is referred to the standard atmosphere 1013250 dynes/cm? as adopted by the International Commission on Weights and Measures [see Rossini (50)] not 1013246 dynes/cm? as used by Birge and DuMond. ® This defined calorie should be distinguished from the calorie of the international steam tables which is used by engineers and defined by 1 I.'T. steam ealorie = 4.18674 abs, joulex. The 15° calorie is given by 1 cals = 4.1855 abs. joules.