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THE JOURNAL OF CHEMICAL PHYSICS VOLUME 35, NUMBER 2 AUGUST,1961
A new potential-energy function has been suggested for the alkali halide molecules,
U = (-&/r) +P exp( -kr2 ) ,
where P and k are constants. Values of a e, "'eX., and the ionic binding energy Di have been derived for the
following three functions: (1) simple Born-Mayer potential, (2) Rittner potential, and (3) the above
suggested potential. The results obtained with the new function are much better than those obtained
with the Born-Mayer potential, but slightly inferior to those obtained with the Rittner potential.
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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
13 L. I<'riedrnan, J. Chern. Phys. 23, 477 (1955). U = (-e 2/r) +Be-r1u (Born-Mayer) (1)
14 N. A. lonov, Doklady Akad. Nauk. S.S.S.R. 59, 467 (1948).
16 T. A. Milne, H. M. Klein, and D. Cubicciotti, J. Chern. Phys.
U = - (e2/r) -[e2(al+a2) /2r4J- (2e2ala2/r7) - (c/r6)
28, 718 (1958).
16 J. Berkowitz and W. A. Chupka, J. Chern. Phys. 29, 653
(1958) .
+A exp( -rip) (Rittner) (2)
17 R. F. Porter and R. C. Schoonmaker, J. Chern. Phys. 29, 2/r)+P
1070 (1958). U= (-e exp( -kr2 ). (3)
18 R. C. Schoonmaker and R. F. Porter, J. Chern. Phys. 30,
283 (1959). In all the three cases we have determined the con-
19W. A. Chupka, J. Chern. Phys. 30, 458 (1959). stants, viz, B, rr, A, p, P, and k by using the conditions
20 A. C. Pugh and R. F. Barrow, Trans. Faraday Soc. 54, 671
(1958) .
21 C. T. O'Konski, J. Chern. Phys. 23,1174 (1955).
(dU/dr)r=r.=O (4)
22 C. T. O'Konski and W. 1. Higuchi, J. Chern. Phys. 23,1175
(1955) . (d2 U/dr2)r.=r.=k., the force constant. (5)
23 T. A. Milne and D. Cubicciotti, J. Chern. Phys. 29, 846
(1958) . We have referred above to the conflicting opinions
24 J. Berkowitz, J. Chern. Phys. 29, 1386 (1958).
26 T. A. Milne and D. Cubicciotti, J. Chern. Phys. 30, 1418 regarding the values of polarizabilities that should be
(1959) . used with such calculation,>. Berkowitz24 has found
26 T. A. Milne and D. Cubicciotti, J. Chern. Phys. 30, 1625
(1959) .
that the differences in polarizability do not change the
27 L. Pauling, Proc. Roy. Soc. (London) A114, 191 (1927). results very much, but somewhat better agreement of
28 J. E. Mayer and M. G. Mayer, Phys. Rev. 43, 605 (1933). vibrational frequencies was obtained with Pauling's
29 J. R. Tessman, A. H. Kahn, and W. Shockley, Phys. Rev.
92, 890 (1953). values of a. Hence we have also used the Pauling set of
30 J. E. Hanlon and A. W. Lawson, Phys. Rev. 113, 472 (1959). values as given in Rittner. The van der Waals attractive
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584 Y. P. VARSHNI AND R. C. SHUKLA
TABLE II. Values of the repulsion constants. 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. The method of calcu-
Molecules (10- cm)
8 (10- cm)
8 (10 16 cm-2) lating (x. and WeXe has been explained in Varshni. 31 The
relevant equations are
LiF 0.2605 0.2739 6.9305 1.4517
LiBr 0.2882 0.3435 7.5302 0.7993 (Xe= -[(Xr./3) +1](6BNw.) (7)
LiI 0.3078 0.3758 8.7714 0.7665
NaCl 0.2852 0.3328 9.2779 0.8322 W.Xe= [~-X2- Y]re2 (W /JLAr.2), (8)
NaBr 0.2939 0.3049 9.5118 0.7597 and
NaI 0.3156 0.3364 9.5909 0.6525
KF 0.2956 0.3184 8.3449 0.8853 Di= -U(r.), (9)
KC] 0.2927 0.3430 10.1115 0.7108
KBr 0.3196 0.3731 9.8266 0.6174 where W =2.1078X 10-16 and
KI 0.3600 0.4199 9.4676 0.5095
RbF 0.2558 0.2938 9.8555 0.9605 X = UIII (re) /Ull (r.)
RbC] 0.3029 0.3558 10.2002 0.6566
RbBr 0.3126 0.3709 10.4216 0.6008 Y = UIV (r.) /Ull (r.).
RbI 0.3589 0.4218 9.8514 0.4880
CsF 0.2319 0.2852 11.1109 1.0103 The experimental data used are recorded in Table I
CsC] 0.3008 0.3614 10.6604 0.6312 and are discussed below.
CsBr 0.3362 0.3964 10.137 0.5371 The expressions for (X" WeX., and D i by the three
CsI 0.3762 0.4414 10.3422 0.4185
potentials are summarized below.
POTENTIAL (1)
constant c can be obtained from
C=!(X1(X2[I2E/ (12+E)], (6) The potential (1) gives
where 12 is the second ionization potential of the alkali (X.=~ ~(r'/CT-3)6B/ (10)
atom, and E is the electron affinity of the halogen atom. 3 CT r./CT-2 We
Varshni2 has given the calculated values of "c" and
these have also been utilized here.
A number of earlier workers have made calculations =~[ (r./CT )4+3(r./CT ) 3-30 (r./CT )2+36 (r./CT ) +18]~
with the Rittner potential (2). Some of these were 3 (r./CT-2) 2 JLAr.2
based on the older data and in some it was assumed (11)
that p is constant for all molecules. As shown below, and
such an assumption is not quite correct. For these Di= (e2/r.) [1- (CT/r.)]. (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. are shown in Tables III, IV, and V.
RITTNER POTENTIAL (2)
Rittner's potential yields the following:
X= (13)
(14)
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POTENTIAL FUNCTION FOR ALKALI HALIDE M OLE:C U LE S 585
TABLE III.
TABLE IV.
L.
/;.
0
we X" WeXe weXe weXe 0.44 o
Molecules (est.) calc. calc. calc. N.
em-I pot (1) pot(2) pot(3) + t<
.42
" Rb
LiF 7.9- 7.787 6.896 6.620 o Cs
LiBr 4.28 b 4.71 3.66 4.12 .40
LiI 3.35 b 3.97 2.997 3.49
NaCI 2.05b 2.14 1. 75 1.89 .38
NaBr 1. SOb 1.56 1.64 1.39
NaI 1.08b 1.23 1.25 1.10
P .36
KF 1.45e 2.25 1.99 1.96
. KCl
KBr
KI
RbF
RbCl
RbBr
1.30b
0.80b
1.3"
0.92b
1.47
0.885
0.621
2.33
1.02
0.576
1.21
0.727
0.507
1.95
0.830
0.465
1.32
0.792
0.553
2.09
0.916
0.520
.34
.32
:
~
,',:/
//
,,
RbI
CsF 1.23 e
0.360
2.54
0.292
1.97
0.323
2.31
.30
,, "
CsCI 0.75b 0.910 0.722 0.824 .28 o ,,"
CsBr 0.416 0.335 0.374 cf
CsI 0.253 0.208 0.229
0.26
F CL Br
a G. L. Vidale, J. Phys. Chern. 64, 314 (1960).
b See works cited in references 4 and 5. FIG. 1. Behavior of the constant p occurring in the Rittner po-
C See work cited in reference 32. tential (2). Broken line is interpolation.
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586 Y. P. VARSHNI AND R. C. SHUKLA
TABLE V.
1.0
\
\ We have followed the policy of taking We and WeXe from
\
\ the same source.
k .9 \""" The binding energy (or the ionic dissociation energy)
D; was calculated from the relation
~"
.8
D;=De+I-E,
.7
~ No
where De is the dissociation energy (obtained from
Gaydon33 ), I is the ionization potential of the alkali
~:.
6
atom (taken from Herzberg 34 ), and E iE the electron
., affinity of the halogen atom (taken from Pritchard35 )
cCs 32 R. F. Barrow and A. D. Caunt, Proc. Roy. Soc. (London)
.4 A219, 120 (1953).
33 A. G. Gaydon, Dissociation Energies and Spectra of Diatomic
0.3 Molecules (Chapman and Hall, Ltd., London, 1953).
F CL 8r I
34 G. Herzberg, Atomic Spectra and Atomic Structure (Dover
FIG. 2. Behavior of the constant k occurring in the potential Publications, New York, 1944).
(3). Broken line is interpolation. 36 H. O. Pritchard, Chern. Revs. 52, 529 (1953).
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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- quantum mechanical calculations predict such a term.
certainties in the Di values. However, it should be noted that the situation on this
point is not so simple. About 30 years ago, 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; ()" varies between form IT(r) exp( -')'r) where IT(r) is a polynomial in r.
0.23 to 0.38 and p varies between 0.27 to 0.45. It is clear Approximation of such an expression merely by an
that the earlier practice of assuming these to be con- exponential term may not be quite satisfactory.
stant has to be abandoned. 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. The behavior of p has been shown in Fig. 1. tential between two atoms having a rare-gas electron
In a group of molecules having the same alkali atom, p configuration. The He-He repulsive potential was first
is seen to increase in the order of F, CI, Br, I, but the calculated by Slater4 and later by several others. A
Na series appears to be an exception. recent treatment is due to Sakamoto and Isiguro. 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. 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, and have reported
Fig. 2. For a given alkali atom, k is found to decrease numerical results for two neon atoms. Their method
as we pass from fluoride to iodide. 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. The
errors. Hence we have shown average percentage errors theoretical results of Sakamoto and Isiguro, Bleick
for both cases: (i) including fluorides and (ii) excluding and Mayel, and of Kunimune were plotted as logY
fluorides. versus r. The points in each case could reasonably ap-
From the average percentage errors it will be ob- proximated by a straight line, indicating that the
served that the resultL obtained with Eq. (3) are much exponential term was satisfactory. However, it may
better than those obtained with Eq. (1) and only also be pointed out that some of the theoretical results
slightly inferior to those obtained with potential (2). are in serious disagreement with the experimental data
For WeXe: As noted above, except for LiF, the re- (e.g., 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).
to draw any conclusions regarding the errors of the The fact that pot.(3) gives a better agreement with
calculated results from the three potentials, hence we experiment than the Born-Mayer potential, does not
have not given the percentage errors. Suffice it to say nece~f,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. (1) > pot. (3) > does a simple exponential term. Rather, the Gaussian
pot.(2). repulsive term appears to simulate the combined effect
Binding Energy D i : We have noted above that most of the terms (b), (c), and (e).
of the experimental values are uncertain by above 4 The available evidence suggests that the simple
kcal, which corresponds to ,,-,3%. As the percentage exponential term is satisfactory for the repulsive
errors using the various functions are also of the same potential alone, while the Gaussian more adequately
order, no strict conclusion can be drawn about the (or fortuitously) takes into account polarization and
relative performances. Nevertheless it may be seen van der Waals effects.
that the average percentage error using potential (3) is ACKNOWLEDGMENTS
less than that using potential (1) but greater than that
using potential (2). The authors are thankful to the Council of Scientific
To summarize, we may say that the results obtained and Industrial Research (India) for financial as-
with potential (3) are much better than those obtained sistance.
with potential (1) but slightly inferior to those ob- One of the authors (Y.P.V.) is highly grateful to
tained with potential (2). Dl. Ta-You Wu and Dr. G. Herzberg, F.R.S. 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, the ex- doctorate Fellowship.
potential term is certainly superior as has been found 38A. Unscild, Z. Physik 43, 563 (1927).
39H. Briick, Z. Physik 51, 707 (1928).
by Varshni2 and by Rice and Klemperer. 5 40 J. C. Slater, Phys. Rev. 32, 349 (1928).
Another argument that has sometimes been ad- 41 M, Sakamoto and E. Isiguro, Progr. Theoret. Phys. (Kyoto)
15,37 (1956).
36 E. C. Baughan, Trans. Faraday Soc. 55, 737 (1959). 42 W. E. Bleick and J. E. Mayer, J. Chern. Phys. 2,252 (1934).
37 D. Cubicciotti, J. Chern. Phys. 31, 1646 (1959). 43 M. Kunimune, Progr. Theoret. Phys. (Kyoto) 5,412 (1950).
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