Derivation of an Internuclear Potential Function from a Quantum Mechanical Model

Ellis R. Lippincott

Citation: The Journal of Chemical Physics 23, 603 (1955); doi: 10.1063/1.1742060
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LETTERS TO THE EDITOR 603
The order of reaction was checked at all temperatures over an
eightfold change of concentration of each reactant. The reaction
was found to be accurately first order in NO and in NzO. An ex-
ample is shown in Table I.
TABLE I. Determination of order in N ,0.
T=924K PNO =100 mm Hg t =30 sec

po" mrn Hg

mmHg Total N,O blank d
P"'l!>
25 0.491 0.059 0.432 1.128
50 1.024 0.164 0.860 1.720
100 2.224 0.460 1.764 1.764
200 4.70 1.29 3.51 1.755
The last column shows that the amount of oxygen formed in
excess of that produced by N20 alone is accurately proportional
to the N20 pressure. The order in NO was obtained by plotting
1/tXlog{[N20]o/[N20Jtl vs PNO at constant PN?O. These plots
were linear in all cases and their slopes are the rate constants, k',
of the catalytic reaction. They are listed in Table II.
TABLE II. NO - N ,0 rate constants.
924
35S1O
OK
970
14to30
1028
6000150
Similar results were obtained from measurements of the rate
of pressure rise. The activation energy now turns out to be 50
kcal. With this lower value, the reaction need no longer be con-
sidered anomalous. The resulting value of 2.5X1O
H
cc mole-
1
secl
for the pre-exponential factor is entirely normal. For the sake of
comparison, the simple collision frequency between NO and N
2
0
at 970
o
K, assuming <TNo=3.6A and <TN"o=4.6A is 3.4X10
14
mole
eel seCl at unit concentrations. This confirms our view, expressed
elsewhere,2 that the importance of the NO catalyzed decomposition
decreases with increasing temperature, since the activation energy
of the uncatalyzed reaction is greater than 50 kcal.
1 F. F. Musgrave and C. N. Hinshelwood, Proc. Roy. Soc. (London)
A13S, 23 (1932).
F. Kaufman and J. R. Kelso (to be published).
Derivation of an Internuclear Potential Function
from a Quantum Mechanical Model
ELLIS R. LIPPINCOTT
Department of Chemistry. Kansas State Col/ege, Manhattan. Kansas
(Received December 28. 1954)
I
Na previous paper a general relation between potential energy
and internuclear distance was proposed having the form
l
E(R) = D.(l-exp( -n!1R2/2R, (1)
where D. is the dissociation energy, R is the intemuclear dis-
tance, !1R=R-R., and n=k.R./D . Also n was evaluated by the
empirical relation
(2)
where no is a constant and (1/lo)A and (l/lo)B are the ionization
potentials of atoms A and B, respectively, relative to those of the
corresponding atoms in the same row and first column of the
periodic table. Here it will be shown that the function (1) and
empirical relation (2) may be derived from a simple quantum
mechanical model through the use of perturbed delta functions.
Delta functions have been previously applied to a number of
electron problems.
2
-
4
Frost has recently formulated a delta-func-
tion model for the electronic energies of molecules, but he gave
no effective means of allowing for interelectronic and internuclear
repulsion.
The model that is proposed here is different from the one used
by Frost
6
in that bond formation is considered to be the result of
the shifting of two atomic delta functions into a molecular delta
function. For the problem of the H2 + ion we use the delta function
V = -g[o(x- (R+a)/2)+o R+a)/2) +x] where x is the inde-
pendent variable along the internuclear axis and a is a function
of R representing the perturbation or shift of the delta function
due to internuclear repulsion. To estimate a it is assumed that
a= J(l/R). An expansion in a power series gives a=ao+at/R
+ .. '. From the solution of the Schrodinger equation, one ob-
tains for the ground state:
and
(3)
(4)
If one chooses the equilibrium bond length for the zero of energy,
and omits e-2c[(alIR)+Rj because it is small when compared to
e-cUadR)+R] and evaluates al from the condition
Eq. (3) becomes identical with the potential function (1), where
(5)
The quantity g has been assigned a value of e
2
as is done with the
II atom problem.'
This model is readily extended to two electron systems and for
the H2 molecule solution of the problem for the ground state
again gives Eqs. (3) and (4) from which again we arrive at the
potential function (1). In this case
D,= (e
4
m/h
2
)e-(nR,+c
ao
l with n=2Ime
2
/h
2
(6)
The calculated and observed values of n, D., k., and x"",. for H.+
and H. are given in Table I.
TARLE I. Calculated and observed properties of H, and H,+ molecules.
H2+ I-I,
calc obs calc abs
n 10-' (cm-
I
) 3.78 3.72 5.345 5.60
D. (kcal/rnole) (from 63.2 64.3 114.3 109.5

k,lO-5 1.59 1.57 5.48 5.73
X,w, 55.3 62. 113.5 117.9
To use the two-electron model for polyelectronic systems,
having intershells of electrons, one must allow for interelectronic
repulsion. By using convenient assumptions, Eq. (1) again follows
with
and
(7)
(8)
On comparing with (2) one has no= (2)f m (e
2
/h') (1 +e-
cao
'). The
factor (1 +e-
cao
') represents the effect of electron repulsion and
varies only slightly for a wide range of molecules and has a value
of 1.150.05. A single value of no should then hold for most
bonds. The calculated value of no is 6.15.10
8
while the average
observed value for most diatomic and polyatomic molecules of
the fourth, fifth, sixth, and seventh columns of the periodic table
is 6.32.10
8
em-I. For heteronuclear bonds 1/10 must be replaced
by (lA+IB)!(IA+IB)o which, when IA and IB are nearly equal,
is making (8) identical with Eq. (2).
1 E. R. Lippincott. J. Chern. Phys. 21. 2070 (1953); E. R. Lippincott
and R. Schroeder. J. Chern. Phys. (to be published).
R. L. Kronig and W. G. Penney. Proc. Roy. Soc. (London) A130. 499
(1931).
a K. Rudenberg and R. G. Parr. J. Chem. Phys. 19. 1268 (1951).
'Fukui. Nagata, and Yonezawa. J. Chern. Phys. 21, 1861 (1953).
5 A. Frost, J. Chem. Phys. 22. 1613 (1954).
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