New Potential Function for Alkali Halide Molecules

Yatendra Pal Varshni and Ramesh Chandra Shukla

Citation: J. Chem. Phys. 35, 582 (1961); doi: 10.1063/1.1731973
View online: http://dx.doi.org/10.1063/1.1731973
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96. 1 (1956). NUMBER 2 AUGUST.29. 860 (1956) j from the Department of Physics. G. Phys. 30. Honig. and We X •• cules. Recently. J. 2615 (1958). Honig. 6 L. Kusch. V. Phys. Rothberg. 27. 981 (1957). C. Chern. (2) Rittner potential. (d) kinetic energy terms representing the difference Considering the crude approximation. ' 10 M. Rev. (e) a short-range repulsion term.) in the expansion of the energy 4 W. J. exp( -r/p). Chern. but slightly inferior to those obtained with the Rittner potential. C. H. neglected). 582 Downloaded 29 Mar 2012 to 200. Frost and J. Soc. interaction and quasi-elastic energy stored in the in. The binding energy is usually represented as con. Frost and Woodson8 have shown a very sisting of the following terms: (a) charge-charge interesting connection between the potential-energy interaction.. and vibrational energy tained by Frost and Woodson are quite satisfactory. 53. For earlier developments. Chern. Phys. Ottawa 2. M. Proc. Phys. Faraday Soc. Townes. On leave 9 R. Similar results ence may be made to Rittnerl and Varshni. from which it is One important limitation of this approach is that the composed (these are usually quite small and may be same curve is predicted for two alkali halide molecules. (b) terms functions of two rare gas atoms and corresponding arising due to charge-dipole interaction.. 2 Some years were obtained by Klemperer and Rice. Chern. Allahabad University Allaha. and found satisfactory results for a number In recent years the existence of polymeric species in of properties of alkali halide molecules. A. which gives a term [-e2/rJ.9-12 mass spectrometric higher powers of (r-r. Trans.794 (1960). with those from Rittner's theory. Mandel. Rittner such as KBr and RbCl. the vapors of alkali halides has been demonstrated in Stitch. India. A exp( -rip) and inverse power b/rn and calculated A proximate the potential energy curves of the alkali halide molecules assuming the molecule to be the rotational constant a e and vibrational constant w. and C.x. P. Rittner. L. However. and the ionic binding energy Di have been derived for the following three functions: (1) simple Born-Mayer potential. expression in terms of (r-re) as obtained from experi. Eisenstadt. 27. Phys. INTRODUCTION used two types of repulsion terms. 629 (1954). M. and P. Stitch. Rice. Miller and P. (London) satisfactory agreement considering the large un. certainties in some of the experimental data.. and G. that the exponential one was better. that this does not give satisfactory values of a. and Townes3 have compared the coefficients of molecular beam experiments. As a first approximation they have put duced dipoles. regardless of which inert gas used a Born-Mayer exponential repulsion term. 4 •5 ago Rittnerl presented a theory of the alkali halide Pauling6 has given a simple treatment of alkali halide molecules in the spirit of the Born-Mayer lattice theory. "'eX. Pauling. J. India (Received December 12. Values of a e. J. Chern. Klemperer. S.797 (1958). dipole-dipole alkali halides whose ions have similar closed shells. J. Proe. 12 M. Canada AND RAMESH CHANDRA SHUKLA Department oj Physics. bad. S.16. M_ Rothberg. Varshni2 8 A. Soc. Kusch. 80. Allahabad. Acad.16. 25. National Research Council. 1960) A new potential-energy function has been suggested for the alkali halide molecules. Phys. Chern. U = (-&/r) +P exp( -kr2 ) . for the two types of repulsion terms and found constituted of ions. ment. H. Redistribution subject to AIP license or copyright. Kusch. Shukla.THE JOURNAL OF CHEMICAL PHYSICS VOLUME 35. Mandel.aip. Varshni and Shukla7 have shown in describing the ionic bond in the alkali halide mole. Phys. refer. rotational. Natl. Phys. The results obtained with the new function are much better than those obtained with the Born-Mayer potential. A. J. Klernperer and S. 19. Woodson. M. P. J. [-e2(at+a2)/2r4-2e2ala2/r7J. 604 (1959). Varshni and R. Varshni. SA. Chern. 618 (1957). Allahabad University. see http://jcp. 5 S. where at U (alkali halide) = (-e 2/r) +U (between rare gas and a2 are the polarizabilities of the alkali and halide atoms having some closed shells as alkali halide ions). * National Research Council Postdoctorate Fellow. and (3) the above suggested potential. J.org/about/rights_and_permissions . Phys. A structure is contained in which ion. 1 E. Chern. 26. 76.132 (1957). Rao. 30.573 (1957). Rice and W. Eisenstadt.1961 New Potential Function for Alkali Halide Molecules Y ATENDRA PAL V ARSHNI* Division oj Pure Physics. where P and k are constants. Am. 1030 (1951).13. uP.oJ. molecules taking into account only terms of the type This theory has been found to be reasonably successful (a) and (e). viz. 52 (1959). exponential NUMBER of attempts have been made to ap. A. Sci. between the molecule and the free iom. the results ob- in translational. They found 7 Y. ions: (c) a van def Waals attraction term [ -c/. India A25. 2 Y.

265 1 0. Mayer and M. Pauling model treatments23 .5269 3. Phys. Pauling. Phys. L.2179 d NaBr 302b 0. Morris. 671 (1958) . Porter and R. Investigations have been made without polariza- CsF 385' 1. 36.4429 d Berkowitz24 has extended the theory of O'Konski and Higuchi and has calculated the molecular structure and NaCl 366b 1. Pauling27 has calculated the polarizability of (1958). T. Chern. but somewhat better agreement of 28 J. J. B. stants.906 d O. a simple argued that the polarizabilities of the ions used in and compact function has obvious advantages in deal- calculations of the energy curve should be chosen to ing with dimers and other polymers. J. Phys. Green and H. +A exp( -rip) (Rittner) (2) 17 R. 30. Milne and D. and J.392d 0. J. E.1004 2.184d tion terms (e.org/about/rights_and_permissions . Lew.451 2. Tessman. Schoonmaker. H. Phys. Phys. Mayer.16. Doklady Akad. 29. 38. Redistribution subject to AIP license or copyright. 605 (1933).2478 2. 23. Hanlon and A. Chern. A.( ) indicate estimated values. Milne and D.072 d also with polarization terms (O'Konski and Higuchi. U = (-e 2/r) +Be-r1u (Born-Mayer) (1) 14 N. Phys. Chupka. 458 (1959). W. and k by using the conditions 20 A.1511 d infrared-active vibrational frequencies of the dimer NaI 258b 0. Klein. H. Schoonmaker and R.036 d Berkowitz24 ) . Phys. F. A. We have referred above to the conflicting opinions 24 J. 21 C. 1. M.667 d 0. In all the three cases we have determined the con- 19W.0475 d alkali halide monomer has been used as the starting RbI (128)b 0.1285 d Cubicciotti25 ) and trimers (Milne and Cubicciotti26 ) KBr 213b 0. B. lonov. Lawson30 ). Roy. Chern.072 d 0. J. model. F. 64.=r. 1625 (1959) . 472 (1959). C.5679 3. J. 54. 846 (1958) . Proc.345 d 0.361d 0. 29. 314 (1960).13-19 and other methods.22 were the w. E.R.2 g 2. J. A. C.g.0236 d model is not wholly satisfactory for the alkali halide . A. the force constant. O'Konski and Higuchi21 .9591 2. J. D. Phys.2107 1 In these studies the potential-energy function of the RbC] 228b 0. Can. However. Phys. RbF 390' 1. E. and D.361 2. Berkowitz. 113. Molecules em-I (105/crn) (10.8648 2. 59. p. 477 (1955). vibrational frequencies was obtained with Pauling's 29 J.378" alkali halide dimer molecules using the Pauling.205 2. F. Klemperer and Rice4. T. Berkowitz and W. (d2 U/dr2)r. Cubicciotti. values as given in Rittner.048d 0. Chern. Phys. Cubicciotti. J.(c/r6) 28. Milne. Tessman. Milne and D. 283 (1959). 29. Kahn. 23. 482 (1960). 718 (1958).=k. Phys. Kahn.1174 (1955). I<'riedrnan. J.l177d molecules.7015 2.(e2/r) -[e2(al+a2) /2r4J. that should be used in the extended potential-energy 1 H.502 d 0.711 d O. d See work cited in reference 3. Chern. Rev. 191 (1927). J. 20 Correspondingly a TABLE 1. Higuchi. and W. R. 1386 (1958). Chupka. (5) 23 T. 467 (1948). Phys. 2/r)+P 1070 (1958). Phys. J. Chern. 1418 regarding the values of polarizabilities that should be (1959) . Chern. Cubicciotti. We have found that it is possible to account for the and Shockley29 have calculated the polarizabilities of potential-energy curve of the diatomic alkali halide ions in ionic crystals from a study of the indices of molecules by using only two tenus: an attractive term refraction of alkali halide crystals (see also Hanlon and [ -e2/r ] and a new type of repulsive term P exp( -kr2). Phys. F. Lawson.25. W. J.16. (London) A114. Chern. 16 J.177d 0. J. C.4586 1. 43. Nauk." Besides its utility for the monomer. 92.3900 3. Geiger.0876d RbBr (166)b 0. The van der Waals attractive Downloaded 29 Mar 2012 to 200. Chern. Vidale. 30. O'Konski. Trans.26) and CsC] 209b 0.S.8 em) em-I first to investigate (NaClh using the Rittner model.821d 0.515 d 0.aip. Phys.1175 (1955) . POT E N T I A L FUN C T ION FOR AL K AL I HAL IDE MOL E C U L E S 583 studies. used with such calculation. 30.5555 d LiI 501 b 0. Faraday Soc. Lew. values of a.(2e2ala2/r7) . A. Porter.945 d 0. Milne and Cubicciotti23 have made calculations on LiF 906. 23. 171 function. Berkowitz24 has found 26 T. J.S. Barrow. values of the polarizabilities of alkali and halide ions e G. that the differences in polarizability do not change the 27 L. results very much. • G. 30. Soc. 545 g 1. Shockley.=O (4) 22 C. T.6703 2. Chern. Chern. 26 T. 16 T. and his values have been checked by Mayer and Mayer28 using spectral data. there has been some disagreement as to the proper C See work cited in reference 32. Phys. We have carried give agreement with the observed molecular dipole.0811 d have also been treated on the basis of the Pauling model KI (173)b 0.0608 d for the monomer. T.9728 2. Cubicciotti. 653 (1958) . Phys.7631 2. Rev. There are considerable differences between this type of tenu is often referred to as the "Gaussian these two sets of values. (3) 18 R. G.7201 2. Phys. the free ions from the theory of the quadratic Stark effect. 890 (1953). O'Konski and W. A.. see http://jcp.22 CsBr (139)b 0. P. Pugh and R. U = .. LiBr 576b 1.171· 0. U= (-e exp( -kr2 ).>. A. Hence we have also used the Pauling set of 30 J. Can. Eisinger. out calculations for the following three potentials: 13 L. it is known that the Pauling CsI (101)b 0.0328 d point. A. Rev. viz. monomers (Varshni and Shukla7). 29. A. KF 400' 1.4929 3. rr. Chern. 1704d 0. S.787 d 0. k. (dU/dr)r=r.7673 2.- number of theoretical investigations have also been made on the subject. On the other hand b See works cited in references 4 and 5.2799· Alkali halide ions of the type M2X+ (Milne and KCl 281 b 0.13. J. Chern.6 have function.

2939 0. and V. (6) The potential (1) gives where 12 is the second ionization potential of the alkali (X. 7 re r.=~ ~(r'/CT-3)6B/ (10) atom.2558 0.2852 0. C./3) +1](6BNw.3430 10. 31 Y. and D i by the three CsI 0.7714 0.Xe= [~-X2.) [1. see http://jcp.3558 10.::\ r.2605 0.).2779 0.4218 9.cm) 8 (10. and . CsBr 0./CT-2 We Varshni2 has given the calculated values of "c" and these have also been utilized here.8322 W. Also2 Di=~{ 1-~)+ 2e «(xl.7597 and NaI 0. Revs.) RbC] 0.) (7) LiI 0. For these Di= (e2/r. A number of earlier workers have made calculations =~[ (r.3029 0. The method of calcu- Molecules (10.3196 0. RITTNER POTENTIAL (2) Rittner's potential yields the following: X= (13) (14) whence (x. Calculations were made for the rotational constant (X" vibrational constant W'X" and the binding energy <T p x k Di for the above three potentials.1109 1. RbI 0. 3 CT r. and WeXe has been explained in Varshni.3964 10.8266 0.6566 RbBr 0.4216 0.2).3762 0./CT )2+36 (r.(CT/r.3184 8.3362 0.Y]re2 (W /JLAr.5909 0. Values of the repulsion constants.3435 7.9305 1.8555 0. 29. can be calculated.8853 Di= -U(r.6312 and are discussed below. P.3422 0.4880 CsF 0.7665 NaCl 0.cm) 8 (10 16 cm-2) lating (x.9605 X = UIII (re) /Ull (r.5118 0. As shown below.13.4414 10. Downloaded 29 Mar 2012 to 200.3156 0.6525 KF 0. Some of these were 3 (r.3449 0.6174 where W =2.3758 8.3328 9.5302 0.3008 0.2927 0.584 Y. Modern Phys.2956 0.4199 9.1078X 10-16 and KI 0.3589 0. (9) KC] 0.2319 0. and E is the electron affinity of the halogen atom.7108 KBr 0.) /Ull (r.3614 10.).3364 9. SHUKLA TABLE II.16.4185 potentials are summarized below. P. Redistribution subject to AIP license or copyright.3600 0.3731 9. (8) NaBr 0.16.2002 0. re 4 r. IV.2739 6.(x2) (!_~)+ 14e2~1(x2(!_~)+ 6C6(!_~) (15) . are shown in Tables III. 6 rc values of p are recorded in Table II and other results are given in Tables III to V.3709 10. (12) reasons we have performed completely new calcula- tions with the best available data for the Rittner The values of CT are given in Table II and other results potential also.aip.3126 0.5095 RbF 0.4517 LiBr 0.6008 Y = UIV (r.5371 The expressions for (X" WeX.8514 0./CT ) +18]~ with the Rittner potential (2).3078 0.0103 The experimental data used are recorded in Table I CsC] 0./CT )4+3(r.3049 9.2938 9.6604 0.4676 0.7993 (Xe= -[(Xr. 664 (1957)..2 based on the older data and in some it was assumed (11) that p is constant for all molecules. POTENTIAL (1) constant c can be obtained from C=!(X1(X2[I2E/ (12+E)]. Varshni. 839 (1959). 31.137 0. VARSHNI AND R. and such an assumption is not quite correct.1115 0.x./CT-2) 2 JLAr.)]. 31 The relevant equations are LiF 0.org/about/rights_and_permissions .2882 0.2852 11. r./CT ) 3-30 (r.

80 -3.5 13. Phys.229 0. L.3 0. b See works cited in references 4 and 5. Morris. lQ4Xa.91 -14.02 0.727 0.27 +15.XIQ4 obs. % calc. d Lew.3 -6.9 LiBr 56.05 -9.997 3.5 1. 36.722 0.0 8. SOb 1. 64.75 +10.374 cf CsI 0. calc. % calc.63 -15. Green and H.45e 2.787 6.0 2. RbI CsF 1.71 3.5 13.7 12.38 NaBr 1. em-I pot (1) pot(2) pot(3) + t< .39 NaI 1..89 +30.30b 4..2 14.56 1.910 0.XI04 a.41 b 66. (1) error pot.99 1.28 b 4.09 +17.32 : ~ .25 1.4 3.23 e 0.00 -9.) calc. FIG.42 " Rb LiF 7.86b 2.org/about/rights_and_permissions .9.i.16.5 b 7.4 4.3 2.314 (1960). L.96 .20b 1.06 +12.2 NaBr 9. 75 1.7 16.90b 9.37 -12. /. POTENTIAL FUNCTION FOR ALKALI HALIDE M OLE:C U LE S 585 TABLE III.83 -1.0 8. L. 314 (1960).253 0.4 NaCl 16. calc.3 100. a. " CsCI 0. Vidale.6 1.95 0. J.5 7.10 P . 0 we X" WeXe weXe weXe 0.75b 0.XIQ4 a.80b 1.8 7.5 1.5 12. Geiger.5 7.2 KCl 7.67 +18.) (17) veniently expressed in terms of another parameter x defined by w.4 3.05 b 4. Phys.83 +20.54 0.51 -7.89 .47 +22.87 -4.=[2X L 78x2-3X3+279X-36J~ (16) (18) 3(x-3)2 J.72 +5.335 0.96 +17.3" 0.89 +15.292 1.05b 2.824 . • N. (2) error pot.9 0. KCl KBr KI RbF RbCl RbBr 1.'.0 8. see http://jcp.17 -2.12 . (3) error LiF 197..576 1.1 Average (excluding fluorides) 18.33 1. Lew.23 1.553 2.32 0.97 0.0 • G.208 0. W.35 c 23.49 NaCI 2.4 14.9 -7.45 -10.5 1.38 +2. 171 (1958).20 +16.04 -5. 38.=[(x2-6x+3) /3(x-3) ] (6BHw.360 2.61 -10.620 o Cs LiBr 4.16 +16.33 +18.97 2.21 0.2 KF 23. % Molecules em-I pot.17 +26.416 0. tential (2). 7.3 -26.00b 15.16. b See work cited in reference 3.0 +17.x.42 -1.1 1.896 6.4 3.14 1.28 o .2 RbI 1.621 2.0 145.19 -0.6 LiI 4O.26 F CL Br a G.520 . Phys.8 CsCI 3. 1.1b 18.41 -10.59 +41.4 KI 2.68b 0.90b 50. 64. Chern.0 6. POTENTIAL (3) Then we have The results for the new potential (3) can be con- a. Redistribution subject to AIP license or copyright.41 +3.35 b 3. Vidale.Ar. Behavior of the constant p occurring in the Rittner po- C See work cited in reference 32.3 RbCl 4.67 -9. Can.18d 17.29 -4.323 2.9 Average % error 18.6 -8.465 1.06 +13.70b 3.3 CsBr 1.0 37.8 3. calc.7 KBr 4.2 TABLE IV.65 +14.13.aip.2 19. e G.92b 1.7 12. J.1 NaI 6.1 CsF 11.25 1.9 11.34 . Can. and Eisinger.4b 10.. Chern.:/ // .37 -6.39 +0. Phys.40 LiI 3.7 RbBr 1.54 -29.81 -14.2 RbF 15.482 (1960).1a 185.10 -6." CsBr 0.830 0.49 +13.66 4.31 +23. Broken line is interpolation.7 -48.64 1.6 47.10b 1.30b 0. Downloaded 29 Mar 2012 to 200.1 37.08b 1.8 4.44 o Molecules (est.8 1.792 0.507 1. J.5 7.70 -2.31 .47 0.5 CsI 0.30 .36 KF 1.916 0.885 0.49 -4.09 0. J.50b 5.22 +13.2 50.

13.4 -9.5 -3.3 107. Barrow and Caunt32 have estimated WeXe from the relation 1.4 117.5 103.4 88. Behavior of the constant k occurring in the potential Publications.0 LiI 130. London. % Di calc.1 -4. •6 atom (taken from Herzberg 34 ).7 -3.4 118.1 131. SHUKLA TABLE V.7 118.0 142.6 132. 33 A.1 123.obs.8 +0.16.8 -4. % Di calc.(l/x)]' (19) III.5 +0. G. New York.4 A219. Klemperer and Rice4 .3 -5. WeXe. (1) error pot.7 101. P.5 -5.5 184.9 NaCI 127. (3) error LiF 177.3 130.8 127.2 84. O. 1953).3 109.3 RbF 135.7 92. 120 (1953).2 +0.5 106. RbBf.8 CsF 133. and of lXe.2 135. D. Roy. k . Chern.7 100.8 97.4 RbI 98.4 +1.2 \ \ the relation obtained from the Morse curve.2 +2.6 125.018. F CL 8r I 34 G.4 130.7 -7.2 -4. (20) \ o Li 1.7 102. 36 H.9 96.2 96.0 KI 101. F. Pritchard.timate together with the sources. I is the ionization potential of the alkali ~:.9 \""" The binding energy (or the ionic dissociation energy) D. 529 (1953). was calculated from the relation ~" .1 KF 131.9 123.0 \ \ We have followed the policy of taking We and WeXe from \ \ the same source.0 +1.5 have used \ 1.1 8 See work cited in reference 33. Revs.4 105.7 +2. WeXe. Caunt.5 CsI 93.4 -8.8 178. (2) error pot.3 135.1 \ \ weXe=[(welXe/6) + B n2/Be 3.6 185.9 1..0 -0. Downloaded 29 Mar 2012 to 200.org/about/rights_and_permissions .1 106. (London) .3 110.9 +3.1 -0.8 -2. Barrow and A. % kcal/mole pot. gators have used semi empirical methods to e<. 1944).2 -5.1 116.0 KBr 109.3 Molecules (Chapman and Hall. 2. VARSHNI AND R. Redistribution subject to AIP license or copyright.013.. these estimated values are believed DATA to be more reliable and consistent.2 RbBr 106.5 LiBr 142.16.3 127.5 136.5 -1.6 -1. RbI.586 Y. of earlier workers. see http://jcp. Herzberg. Values WeXe and to adjust We accordingly. Calculated mated by Rice and Klemperer. respectively.1 -0.0 -5.1 94.0 -7. Soc.=De+I-E. and CsI given here are those esti- Values of k and x are tabulated in Table II.7 121.8 -4. (3).8 -5. Molecules D.7 134. The We values for KI.8 97.8 D.3 \ A Rb \ \ o Cs On the other hand. are given in Table I. 5 Though experimental results for lXe.7 108. \ \ 1.4 \ \ • No However.3 -5. Dissociation Energies and Spectra of Diatomic 0. Proc. Broken line is interpolation. Gaydon.3 CsCI 107. IV.3 85.8 -3. calc. and V.0 +3. C.9 NaBr 124.7 ~ No where De is the dissociation energy (obtained from Gaydon33 ).4 132.8 130. Atomic Spectra and Atomic Structure (Dover FIG.9 RbCI 111. CsBr.4 111.5 +3.6 -4.3 -1. affinity of the halogen atom (taken from Pritchard35 ) • cCs 32 R. 5 It is very difficult to evaluate WeXe from the experimental data. so investi- The experimental data used in the calculations.6 128.1 97. Ltd. 1.4 KCI 113.9 -3.6 -0.9 -2.1 104.5 q xeMA!=0. and binding energy D i are given in Tables Di= (e 2/re) [1.6 102. and Di along with percentage errors values for these molecules are available from the work are shown in Tables III to V. 52.0 -4.4 Average % error 4.4 -4.1 -5." D.5 -4.1 +0.4 +0.5 -4.7 CsBr 103.8 4. (21) \ \ 1.7 +2.7 -7.5 108.2 -1. the constant in this relation IS rather un- \ \ + K certain and it may be as high a" 0.5 NaI 114.8 +4. .aip.6 -3.7 -6.0 -4.7 101.8 109.7 132. and E iE the electron .3 -6.7 -0.6 112.

It is clear Approximation of such an expression merely by an that the earlier practice of assuming these to be con. E.16. ()" varies between form IT(r) exp( -')'r) where IT(r) is a polynomial in r. J.org/about/rights_and_permissions . recent treatment is due to Sakamoto and Isiguro. Baughan36 has al'lo recently Further evidence on this point is available from the concluded that ()" varies by about 15% for different quantum-mechanical calculations of the mutual po- molecules. while the Gaussian more adequately order. Z.38 and p varies between 0.37 (1956). the re. tential between two atoms having a rare-gas electron In a group of molecules having the same alkali atom. see the comparison of the theoretical and experi- ported values are estimated ones and it is not possible mental results in the paper of Sakamoto and Isiguro). Chern. (Kyoto) 15. 36 E. quantum mechanical calculations predict such a term. Phys. 55. Briick. versus r. One of the authors (Y.252 (1934).P. but the calculated by Slater4° and later by several others.45. CI. 2. For a given alkali atom. 31. C. Redistribution subject to AIP license or copyright.V. Trans. Downloaded 29 Mar 2012 to 200. proximated by a straight line. As the percentage exponential term is satisfactory for the repulsive errors using the various functions are also of the same potential alone. Herzberg. I. Hence we have shown average percentage errors theoretical results of Sakamoto and Isiguro. Phys.-. Progr. Bleick for both cases: (i) including fluorides and (ii) excluding and Mayel. The behavior of p has been shown in Fig. Z. (1) and only also be pointed out that some of the theoretical results slightly inferior to those obtained with potential (2). doctorate Fellowship. Cubicciotti. it may better than those obtained with Eq. 707 (1928). and (e). 737 (1959). which corresponds to . (3) > does a simple exponential term. 349 (1928). 41 It is interesting to note that parallel results have also Bleick and Mayec42 have used a generalized Heitler- been obtained in the case of alkali halide crystals. Mayer. 5 40 J. potential term is certainly superior as has been found 38A. 37 D. However. 41 M. 39H.412 (1950).3%. London method to compute the repulsive potential (Cubicciotti37 ) • between two atoms (or ions) having closed-shell con- The behavior of the constant k has been shown in figurations of eight electrons each. The points in each case could reasonably ap- From the average percentage errors it will be ob. Kunimune. of the experimental values are uncertain by above ±4 The available evidence suggests that the simple kcal. Baughan. About 30 years ago. Their method as we pass from fluoride to iodide. hence we experiment than the Born-Mayer potential. 0. that the average percentage error using potential (3) is ACKNOWLEDGMENTS less than that using potential (1) but greater than that using potential (2). the Gaussian pot. 1.. are in serious disagreement with the experimental data For WeXe: As noted above. Phys. J. indicating that the served that the resultL obtained with Eq. E. k is found to decrease numerical results for two neon atoms. Isiguro. Sakamoto and E. Rather. Chern. it should be noted that the situation on this point is not so simple. repulsive term appears to simulate the combined effect Binding Energy D i : We have noted above that most of the terms (b). However.23 to 0. F. 2. and of Kunimune were plotted as logY fluorides. Physik 43. (Kyoto) 5. we may say that the results obtained and Industrial Research (India) for financial as- with potential (3) are much better than those obtained sistance. Bleick and J. C. 43 M. The He-He repulsive potential was first is seen to increase in the order of F. Unscild. A Na series appears to be an exception. by Varshni2 and by Rice and Klemperer. Suffice it to say nece~f. p configuration. no strict conclusion can be drawn about the (or fortuitously) takes into account polarization and relative performances. Dl. Theoret. certainties in the Di values. exponential term may not be quite satisfactory.) is highly grateful to tained with potential (2). G. Ta-You Wu and Dr.27 to 0. The errors.(2). POT E N T I A L FUN C T ION FOR ALK ALI HAL IDE MOL E C U L E S 587 Most of the De values are uncertain by about ±4 vanced in support of the exponential term is that the kcal and cOI'sequently there are corresponding un. Theoret. 1646 (1959). Slater. Physik 51. to draw any conclusions regarding the errors of the The fact that pot.aip. stant has to be abandoned. for their Certain points regarding the form of the repulsive kind interest in the work and further thanks the term may be noted: National Research Council for the award of a Post- As compared to the inverse-power term. 42 W.16. except for LiF.arily mean that a Gaussian term more accurately that the calculated values by the three potentials describes the repulsive part of the potential than usually lie in the following order: pot. Unsold 38 DISCUSSION and Bruck39 showed that the repulsive energies between It will be noted from Table II that neither ()" nor p a point cation and a closed-shell anion should be of the are constant for all of the molecules. (1) > pot.(3) gives a better agreement with calculated results from the three potentials. and have reported Fig. The authors are thankful to the Council of Scientific To summarize.g. 563 (1927). Rev. (3) are much exponential term was satisfactory. (e. Another argument that has sometimes been ad. the ex. Faraday Soc. Nevertheless it may be seen van der Waals effects. 32.13. see http://jcp. Phys.S.R. (c). Phys. does not have not given the percentage errors. Progr. with potential (1) but slightly inferior to those ob. Br. ha'l been used by Kunimune43 to calculate the re- For a e : The fluorides appear to give high percentage pUlsive potential in the case of two argon atoms..