Energy Calculations of Multiple HydrogenAtom Systems by VB and MO Methods

Roland S. Barker, Richard L. Snow, and Henry Eyring

Citation: The Journal of Chemical Physics 23, 1686 (1955); doi: 10.1063/1.1742411
View online: http://dx.doi.org/10.1063/1.1742411
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 THE JOURNAL OF CHEMICAL PHYSICS VOLUME 23, NUMBER 9 SEPTEMBER, 1955

Energy Calculations of Multiple Hydrogen-Atom Systems by VB and MO Methods*

ROLAND S. BARKER, RICHARD L. SNOW, AND HENRY EYRING
Department of Chemistry University of Utah, Salt Lake City, Utah
(Received December 28, 1954)

The equivalence of complete valence bond (VB) and of total configuration interaction molecular orbital
(CIMO) methods has often been discussed. The two methods give identical expressions for H 2. Treatment
of H2 by the method of Coulson and Fischer also gives the same result. An extension of this method of semi-
localized orbitals to the H3+ and H3 systems is attempted and found to be unsatisfactory. This indicates that
a single configuration treatment, however general the molecular orbitals may be, is a poorer approximation
than either the extended VB or CIMO treatments.
R. Taylor's exact integral (LCI) molecular orbital treatment for linear H4 is compared with the exact
integral covalent bond (HL) method. A single structure of the latter method gave a ground-state energy of
-57.02 ev while the two covalent structure treatment gave -58.59 ev. An energy of -55.64 ev is reported
by Taylor using the best single MO configuration while he found an energy of only - 56.40 ev using six of
twelve possible MO ground-state configurations. It appears in view of the equivalence of the refined forms
of the two treatments that the omitted higher energy configurations contribute more strongly to the ground-
state energy than the lower energy ones. This indicates that low energy is not a good criterion for inclusion
of configurations in a limited configuration interaction treatment. Recent work by A. Pullman on butadiene
supports this conclusion.

1. INTRODUCTION and Fischer9 treatment of H2 has not received the same

R ECENT developments in molecular quantum
mechanics have been confined in the main to
refinement and use of the valence bond, VB, and molecu-
lar orbital, MO, approximations. Each of these methods
has its own limitations and the particular problem
under consideration seems to determine which method
should be applied. Comparison of exact calculations by
the two methods has been a stimulus to theoretical
development, but until recently precise calculations for
molecules of greater complexity than H2 have usually
necessitated mathematical approximations of uncertain
magnitude.
Exact evaluation of some difficult multicenter inte-
grals1- a in these complex problems has now allowed a
careful consideration of a few multiparticle systems. 4- 6
In this paper VB and MO wave functions for multi-
hydrogenic systems are compared. Numerical results
for the ground-state energy of the linear H4 system are
also discussed.
2. EQUIVALENCE OF VB AND MO TREATMENTS
IN POLYATOMIC SYSTEMS
The equivalence of the VB treatment to the complete
M 0 trea tmen t has been discussed before. 7 ,8 Equivalence
of these formulations has been specifically examined for
the Ha+ and Ha systems. 4.6 The possible equivalence of
the extended VB method to refinements of the Coulson
* This work was assisted in part by a grant from the National
Science Foundation.
1 Hirschfelder, Eyring, and Rosen, J. Chern. Phys. 4, 121 (1936).
2 M. P. Barnett and C. A. Coulson, Trans. Roy. Soc. (London)
A243, 221 (1951).
3 R. S. Barker and H. Eyring, J. Chern. Phys. 21, 912 (1953).
4 Walsh, Moore, and Matsen, J. Chern. Phys. 18, 1070 (1950).
6 J. M. Walsh and F. A. Matsen, J. Chern. Phys. 19,526 (1951).
6 R. G. Pearson, J. Chern. Phys. 16, 502 (1948).
7 A. Meckler, J. Chern. Phys. 21, 1750 (1953).
8 P. O. L6wdin, Quarterly Progress Report of the Massachusetts
Institute of Technology Solid-State and Molecular Theory Group
(January, 1952).
consideration. Some attempts4,5 have been made in this
direction, but these have not proved completely satis-
factory. The semilocalized orbital theory of Mueller and
Eyring lO may be considered from this point of view.
Consideration of electron repulsion has been included in
their single configuration treatment with improved
results. However the decomposition of their semilocal-
ized orbitals into the proper atomic orbitals at infinite
separation only partially duplicates Coulson's result
with H 2. Even for Ha+ and Ha calculations have not
met with equivalent success. In view of such work we
have analyzed the wave functions of Ha+ and Ha by
decomposing the most general unsymmetrical molecular
orbital wave functions for these systems into the
constituent atomic orbitals. The possible equivalence
of this MO treatment to the VB treatment for these
simple systems is thus tested. The wave function for
the linear Ha+ system may be formulated as
(2.1)
where,
A =}Qa+A 2b+AaC
A I = J-L1a+J-L 2b+J-Lac.
Upon simplification of expression (2.1) and equating
like terms to those obtained in the extended VB treat-
ment (covalent plus ionic terms) one has the incon-
sistent equations,
C1= A1J-L2+A2J-La= A2J-L a+ A1J-L 2
= A2J.L1+A 3J-L2 = AaJ-L2+A 2J.L1
C 2 = AlJ.L 1+ AaJ-L 3= AaJ-La+A1J-L1 (2.2)
C 3= 2A 1J-L3 = 2A aJ-L 1
C 4 = 2A 2J-L2.
9 C. A. Coulson and I. Fischer, Phil. Mag. 40, 386 (1949);
C. A. Coulson, Trans. Faraday Soc. 33, 1479 (1937).
10 C. R. Mueller and H. Eyring, J. Chern. Phys. 19, 1495 (1951).

1686

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 ENE R G yeA Leu LA T ION 5 0 F M U L TIP L E H - AT 0 M 5 Y 5 T EMS 1687

Numerical values of the C's were obtained by Hirsch- is made in the usual way.12 Thus one obtains,
felder ll using the complete VB wave function,
H 11 = f ~IJC~ldT = 8aWabab+4aWc2dZ+ 8adbcacac
- 8a2abacbc- 8adb2acab- 4a2c2acac
~=Cl{ (:;)-(:~)+(:;)-(;~)} - 2a2a2bcbc- 2adadbW+4acacacac
+ 4adadbcbc - 8acacabab+ 4abababab. (3.4)
(2.3)
H 12 = H 21 = 8a2bdc2db+ 8a2bdcbdc- 4aWcddc
+C2{ (:;)-(:~)} - 4a2bccddb - 2a2b2c2dZ+ 8acb2cdda
- 2a2bccbdZ+8abbccdda- 2adb2c2da
- 4adbccadb- 2abbdcadc- 2acbdcadb
+C3{ (::)+(;~) }+C4(:;)' - 2abbacddc- 2adbccbda- 2acbacddb
-4adb2cadc. (3.5)

No consistent values of AI, A2, Aa, J.ll, J.l2, and J.la could be H 22 = f.J;2JC~2dT=4aWc2dZ-4a2b2cddc+4abbacddc
found. A similar analysis was made for the H3 molecule +4adb2c2da+ 4a2bccbdZ- 4a2bdc2db
and again inconsistent parametric equations were ob- - 4a2bccddb - 4a2bdcbdc+4acbacddb
tained. Thus it has been concluded that no single + 4abbdcadc+4acbdcadb - 4adb2cadc
configuration treatment for even these simple molecules - 4acb2cdda+4adbccbda- 4acbdcbda
will give results equivalent to the complete VB treat- -4adbacbda. (3.6)
ment or the complete MO treatment. The atomic orbital integrals are written symbolically,
3. ENERGY CALCULATIONS FOR THE LINEAR fa(1)a(2)b(3)b(4)IJCld(1)d(2)c(3)c(4)dT
H, SYSTEM = (aabb IJC I ddcc) = adadbcbc.
a. Valence Bond Calculation They may then be easily expressed ll in terms of com-
The wave functions for the covalent structures of the posite integrals of the types Iac=fa(n)c(n)dTn (over-
ground-state H4 linear symmetrical system may be lap), K a, bc=f(l/ran)b(n)c(n)dTn (nuclear attraction),
represented by Lad, bc= f (1/r nm)a(n)d(n)b(m)c(m)dTndTm (electron re-
pulsion), and Tab=fa(n) l_jV'21 b(n)dTn (kinetic en-
ergy). This kinetic energy integral may be further
a bed) (a bed) simplified to an expression in terms of the elemental
~l =~ab, cd= ( -
a{3a{3 {3aa{3 overlap, attraction, and repulsion types listed.
The needed numerical evaluations of the elemental
_ (a be d)+(a bed) (3.1) integrals for the internuclear distance selected for the
a{3{3a {3a{3a H4 system are all tabulated by Taylor,13 This selected
internucleardistanceisR=Rab=Rbc=Rcd= 1.4 a.u. The
a bed) (a bed) values, given in electron volts, were obtained by series
.J;2=.J;ad. bc= ( - methods1,2 and are believed to be accurate to the given
aa{3{3 {3aa{3 four significant figures.
Results obtained for the linear symmetrical H4
_ (a be d)+(a bed). (3.2) system give a ground-state energy of -57.02 ev
{3a{3a {3{3aa for the single covalent structure represented by the
VB wave function ~1(3.1) and an energy of -58.59
The function for ~ac, bd need not be considered as it is ev for the complete covalent-bond representation,
easily shown to be a combination of (3.1) and (3.2). ~=kl~l+k2~2'
The notation and symbols are those used previously.
The wave function for the VB covalent structural b. Molecular Orbital Calculation
approximation is then, .J;= kl~l+kzl//2. The complete
Hamiltonian operator for the system is, The MO treatment of the linear symmetrical H4
system is given explicitly by TaylorP The separate
4 d d,4 4 phases of the theory are therefore not examined in
JC= - j L V'n2 + L R 1p-l- L rln-1+ L rmn-1 • detail. In the examination of the configuration inter-
n=l l=a,n=l n>m=l action MO approach however consideration might
(3.3) well be given to the specific MO's used.
The four molecular orbitals (MO's) for the H4
The ground-state energy may be computed by solution
system are constructed from linear combinations of is
of the usual second-order secular determinant. Reduc-
atomic orbitals (LCAO) considered to be associated
tion of the matrix elements to atomic orbital integrals
12 R. S. Barker and H. Eyring, J. Chern: Phys. 22, 1182 (1954).
11 J. O. Hirschfelder, dissertation, Princeton University (1935). 13 R. Taylor, Proc. Phys. Soc. (London) 64, 249 (1951).

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 1688 BARKER, SNOW, AND EYRING

with the four nuclei ct, CB, e, and :0. These
orbitals may be designated, as a(n), ben), c(n), and
den). The orbital d when occupied by electron n is
thus d(n)= (Zi/Tr)!e-Zdrdn. The molecular orbitals may
then be formulated as,
A (n)= kaAa(n)+kbAb(n)+kcAc(n)+kdAd(n)
B(n) = kaBa(n)+kbBb(n)+kcBc(n)+ kdBd(n)
C(n) = kaca(n)+kbcb(n)+kccc(n)+kdcd(n)
D(n) = kaDa(n)+hDb(n)+kcDc(n)+kdDd(n).
The capital letters L(A, B, C, or D) represent the differ-
ent molecular orbitals, the small letters (a, b, c, or d) the
atomic orbitals and the k1L'S the appropriate coeffi-
cients. Various techniques for obtaining numerical
values for these molecular orbital coefficients, k1L, have
been used. One frequently favored, the Roothaan
technique,14 proceeds by way of an iterative self-
consistent field (SCF) method employing a matrix
procedure. Other simpler "inconsistent" coefficients are
used by Taylor.1 3 The question of comparative worth
of such techniques will be commented upon later.
Compounding the MO's of the system into "spin-
orbital composition functions" parallels development
with the valence-bond method. 15 ,16 Definition of a
particular so-called spin-orbital composition function,
"antisymmetrized product (A.P.)" or "Slater determi-
nant" follows. The various notational forms are,
1/;= LP.( -1)v(AahCAi1hCBaMB{1)4
(Aah (Ai1h (Ba) 1 (Bi1h
(Aa)2 (Ai1h (Ba) 2 (Bi1h
= (4 !)-!
(Aa)3 (A{1) 3 (Bah (B{1)3
(Aa)4 (A{1)4 (Ba)4 (B{1)4
system define the following spin-orbital composition
functions <l>n.
These spin-orbital composition functions, <l>n, of
Table I may be compounded into configurations by the
usual considerations. Thus the l~g configurations are,
(3.7)
'Ii VII =<1>7-<1>6= (A A B D) _(A A B D)
ai1ai1 ai1i1a
"'VIII =<1>9-<1>10, 'iiI X=<1>11- <1>12, 'lix = <1>13-<1>14,
'Ii XI = <1>15 -<1>16 - <1>17+<1>18
"'XII = <1>15+<1>18-<1>19-<1>20'
Six of the foregoing l~g configurations were used by
Taylor13 in a limited configuration interaction (LCI)
treatment. Increasing order of orbital energies is indi-
cated by the MO series A, B, C, and D (Taylor's i, j, k,
and I). Orbitals A and C (i,k) are symmetrical (O'g)
while Band D (j,t) are antisymmetric (O'u) with respect
to reflection in the plane normal to the line of protons
at the geometrical midpoint. Numerical values for the
MO coefficients, k1L, obtained by usual techniques are
(3.8) given in the appendix of Taylor's article.
The wave function for configuration interaction may
be written,
(3.11)
(3.9)
The coefficients, K N , and the ground-state energy may
be found in the usual way from the Nth-order secular

=(AABB). (3.10) TABLE I. Spin-orbital (u g ) composition functions for H 4 •

ai1ai1
Occupied Orbitals A (g) B(u) erg) D(u)
The foregoing notations (3.8), (3.9), and (3.10) explain Cap. letter Taylor's or or or or
notation notation i j k I
in part the profusion of names used in the literature.
(A2.82) (i2 j2) a(3 a(3
From the first representation as "a linear combination (A 2O) (i 2k2) a{3 a(3
of products" the antisymmetric nature of the function (A 21)2) (i 212) a{3 a(3
(.820) (j2k 2) a(3 a(3
with electron exchange is apparent. The "expanded (J32D2) (j212) a(3 a(3
Slater determinant notation" (3.9) makes satisfaction (01)2) (k 212) a(3 a(3
of the Pauli principle obvious from the laws of determi-
(A2BD) (i2jl) a(3 a (3
nants. The third notation (3.10) stresses the particular a(3 (3 a
spin-orbital assignment. Each such "spin-orbital com- (AB2C) (ij"k) a a(3 (3
position function" is associated with a definite assign- (3 a(3 a
(BOD) (jk 21) a a(3 (3
ment of the spins to each component molecular orbital. (3 a(3 a
These functions singly or linearly combined give the (AC1)2) (ikI2) a (3 a(3
so-called molecular-orbital configurations. (3 a a(3
For the linear symmetrical H4 system allowed alloca- a {3 a (3
tion of the electrons to the molecular orbitals of the a (3 (3 a
(ABCD) (ij kl) (3 a a {3
14C. C. J. Roothaan, Revs. Modern Phys. 23, 69 (1951). (3 a (3 a
15 J. C. Slater, Phys. Rev. 38, 1109 (1931). a a (3 (3
18 Eyring, Walter, and Kimball, Quantum Chemistry (John (3 (3 a a
Wiley and Sons, Inc., New York, 1944), p. 190 ff.

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 ENE R G yeA Leu L A T ION S 0 F M U L TIP L E H - AT 0 M S Y S T EMS 1689

determinant, the secular equations, and the trial func- TABLE II.
tion normalization condition. Taylor's LCI treatment
N = 6, used the six lowest energy configurations. With System and type treatment
Energy of
system (ev)
such treatment using simple inconsistent MO's he
Single H atom -13.537
obtained a ground-state energy of E= -56.40 ev. The Molecular H2
lowest single configurational energy of this set was Experimental (R= 1.4 au) -31.95
E= -54.11 ev. A better single configuration energy SC-VB (Covalent structure) R= 1.66 -30.35
SC-VB Wang refinement (R= 1.45) -30.96
was obtained using the single determinant (SCF) SC-MO (R= 1.6 au) -29.89
MO's. Such treatment gave E= -55.64 ev. The results TCI (R= 1.6 au) -30.43
of both MO and VB approximations are given in Table TCI (R= 1.4 au) -30.03
Four free H atoms -54.148
II. The usual abbreviations, (SC-MO) single-configura- Two H2 molecules TCI (R= 1.4 au) -60.06
tion molecular orbital, (TCI) total configuration inter- Linear symmetrical H4 (R= 1.4 au)
SC-MO -54.11
action, and (LCI) limited-configuration interaction SC-MO (SCF) -55.64
are used in the table. LCI-MO (6 of 12) -56.40
Comparison of the results for the H4 system given in SC-VB (Single covalent structure) -57.02
SC-VB (SCF Wang-like refinement) -57.03
Table II disclose that the best single-configurational LCI-VB (2) Both covalent structures -58.59
MO treatment is 2 ev poorer than the best single-
covalent structural VB result. Further the LCI-MO
treatment using the six lowest energy configurations is present position with respect to a choice of VB or MO
3 ev poorer than the LCI-VB treatment using just the approximation. The paramagnetism of the ground
two covalent structures. As the TCI treatments of state of O2 is still best accounted for by the MO treat-
both VB and MO approximations are equivalent, one is ment while some individual energy calculations of the
led to conclude that for this system a simple VB treat- VB treatment are best. The choice must still be made
ment is preferable to the simple MO treatment. The for the particular problem under consideration.
poor LCI-MO results may be due to the inclusion of
too much "ionicity" in the low-energy MO configura- 5. OTHER POSSIBLE REFINEMENTS
tions. The substitution of neglected higher energy MO A common type refinement for simple hydrogen-
configurations for the low-energy ones in the LCI treat- atom-containing systems of both VB and MO type
ment might give a better result. Recent work by treatments is inclusion of a so-called "effective charge"
Pullman17 on butadiene indicates that such may be the parameter Z. Taylor rightly decided on the basis of
case. A full configuration interaction treatment of the previous calculations by Coulson and on the basis
nine 11:0 functions of butadiene show the ground-state of the unequal placement of the nuclei, a and d at the
energy to consist of 87% of the lowest energy configura- end and band c in between, that such a Wang-like
tion, and of 5.5% and 1% of the highest and next high- refinement would alter the energy of the H4 system
est energy configurations respectively. Calculations of very little. Similar reasoning would apply to the VB
the dipole and other properties are even more affected treatment.
by the high energy configurations. Another possible refinement of the treatments might
The results of our work and of Pullman's paper lend include a more realistic internuclear distance param-
emphasis to the recent melancholy conclusion of Coul- eter. The experimental internuclear H2 distance R= 1.4
son, Craig, and Jacobs18 that "It appears beyond any au is smaller than the best distance minimization values
doubt, that configuration interaction plays a significant of comparable H2 calculations. For the loosely bound
role" and that "there appear to be no simple rules for H4 system the internuclear distance R would certainly
determining in advance which (MO) configurations be greater. However, in view of the difficulty in re-
will interact most strongly with one another." The poor evaluating the difficult multicenter integrals and in
energy comparison of the "best" single MO configura- view of the fact that this linear H4 system's greatest
tion of the H4 system with the simple Heitler-London importance would seem to be in testing various types
type VB calculation supports the further conclusion of computations such a refinement has not been
that control of "the extent of interaction by such means attempted.
as a better choice of basic MO's is not really satis-
factory." Such conclusions, however, do not alter the ACKNOWLEDGMENTS
We should like to thank M. Krauss and A. L.
17A. Pullman, J. chim. phys. 51, 188 (1954).
18Coulson, Craig, and Jacobs, Proc. Roy. Soc. (London) A206, Wahrhaftig, Chemistry Department, University of
308 (1951). Utah for helpful discussions of phases of this problem.

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