Michael J. S.

Dewor
and J6zsef Kelemen
The University of Texas at Austin
Austin, 78712
1I LCAO MO Theory Illustrated
by Its Application to H,

A few years ago ab initio calculations,

i.e., ones involving rigorous solution of some approxi-
mate formulation of the Schrodinger equation, could
be carried out only for the simplest molecules, and even
these taxed the capabilities of existing digital com-
puters. Recently, however, this kind of approach has
been extended to molecules large enough to be of chem-
ical interest, partly through the development of more
powerful computers (e.g., the CDC 6600) partly potential energy due to their coulombic interaction;
through technical improvements in computationa~ the Hamiltonian'operator (H) is therefore a sum of the
~rocedures. corresponding operators, i.e.
These calculations are based on the Roothaan
method, an approximation to the Hartree-Fock self- where the kinetic energy operators for nuclei (TN)and
consistent field (SCF) treatment in which the individ- electrons (TE) are given by
ual orbitals $p are approximated by linear comb'ma-
tions of a set of assumed functions +r
*,. = C a,.,+; (1)
i M and m being the masses of a proton and an electron,
The coefficients aptare found by solving a set of simul- respectively. The internuclear (GNN), nuclear-elec-
taneous algebraic equations (Roothaan's equations), tronic (GNE), and interelectronic (GEE) potential
derived by the variation method. The basis set func- energies are given by
tions 4%are usually a: set of AO's of the component
a t o m (LCAO approximation). By using a sufficiently
large basis set, this approach can apparently he made
to give results virtually identical with those that would
be given by a rigorous Hartree-Fock treatment.
While the results of such calculations are subject to
large errors, due to the neglect of electron correlation
inherent in the SCF approach, they are already proving We now assume that the motion of the electrons can
of interest in a number of connections and there is also be represented by an elect.ronic wavefunction T that
reason to believe that the correlation problem may be depends on the positions of the nuclei but not on their
solved in due course. In the meantime semiempirical velocities (Born-Oppenheimer approximation) ; this
treatments, based on the Roothaan approach, are
proving very promising. It therefore seems clear that TN,or that TN* is neghgible.
*
is equivalent to the assumption that commutes with

an understanding of these procedures will soon become In that case

essential to anyone concerned with the progress or Q = 93 (5)
application of chemical theory.
Several good accounts of the Roothaan method where the electronic wavefunction is a function of the
are now available in book form (1); these, however, electronic coordinates, the nuclei being fixed, and the
have usually been formal in nature and have lacked nuclear wave function % is a function of the positions
illustration by sufficient specific examples. The pur- of the nuclei. The total energy @ for a given fixed
pose of this paper is to remedy this deficiency by a position of the nuclei is then
detailed discussion of the hydrogen molecule, using the
SCF LCAO MO formalism.
LCAO MO Formalism for H2 where EE is the total energy of the electrons moving in
a fixed potential field due to the fixed nuclei. Thus
The hydrogen molecule is composed of two protons
(A and B) and two electrons (1 and 2); we use the fol-
lowing notation for the interparticle distances. The
total wave function *
of H2 is an implicit function where the electronic Hamiltonian HE is given by
of the twelve coordinates (XA,y ~ a;
, XB, YE.,ZB; XI,y ~z~
, TE + GNE + GEE
HE = (8)
x2, y, z2) of the four particles. The total energy is a
sum of the kinetic energies of the particles and the we can write this in the form
494 / Journal of Chemical Education
where the core Hamiltonians HIC and HzCare given by

where the overlap inteyral Slzis given by

The core Hamiltonian HC represents the sum of the Sn = J+hdr (19)

kinetic energy of an electron and its potential energy The unit of energy in a.u. is the Hartree
due to attraction by the nuclei; it is therefore a fnnc-
e'
tion of the coordinates of one electron only. 1 a.u. (Hartree) = - = 27.210 eV = 627.71 kcal/mole (20)
a0
Next we make the orbital approximation, which
assumes that the motion of each clectron i can he repre- This is twice the ionization potential of a hydrogen
sented by an individual one-electron wave function atom. I n a x . the core operator HC (eqns. (10) and
$*. The probability of finding the electron in a given (11)) and the operator GEE(eqn. (4)) become
volume element drr is then $tzd7c. This approxima- 1 --
1 --
1
tion thus involves neglect of electron correlation, i.e., HC = -.vI (21)
2 ra IB
the tendency of electrons to correlate their motions in
such a way as t o minimize their mutual repulsions.
The one-electron functions mnst also include a descrip-
tion of the spin of electrons; we write them as spin The two electrons in HZ can occupy the MO's $I and
orbitals where Gi is a function of the space coordi- $,in six different ways
nates (xi, y,, zi)and the spin function oi has one of two
values ( a or B). The electronic wave function for HZis
then written as a Slater determinant

'x, X, X6 lxg
The superscript denotes the electron occupying the
spin orbital in question.
The final approximation is to write the orbitals $, Each of these configurations is represented by a Slater
as linear combinations of basis set functions $, (eqn. determinant (eqn. (12))
(1)) which are usually taken to be SCF AO's of the in-
dividual atoms. The coefficients a,< are normally
found by solving a set of simultaneous algebraic equa-
tions (Roothaan equations). I n the case of Hz, the
problem is simplified by the presence of a plane of
symmetry bisecting theline joining the nuclei; the MO's
and $2 mnst be symmetric, or antisymmetric, for re-
flection in this plane.
Electronic Wave Functions of H2
We will use a minimum basis set, i.e., a set of AO's
corresponding to the naive conventional picture of
inner and valence shell AO's; in HZ this corresponds
t o the 1s AO's of two atoms, given by

(29)
The shorthand notation, e.g., ll+B1ll is self-explana-
tory; here the overbar denotes p spin, lack of it a spin.
where r* and rs are the distances of the electrons from Four of the determinants ('XI, 3xa2axs,'xs) can, as
their respective nuclei, measured in atomic units (a.u.) indicated, be factored into products of a space part and
a spin part; these are all eigenfnnctions of the opera-
tors S. (representing the component of spin momentum
where a. is the radius of the smallest Bohr orbit for along the z axis) and S Z (representing the square of
hydrogen. I n this system of units, which we will use the total spin) and so can serve as representation of HZ
henceforth, the mass of the electron and the electronic (for details see reference ( I c ) ) . Thus
charge are taken to be unity. S2('x,) = Sy'x,) = S*('x,) = S,('xs) = 0 (30)
From symmetry (see above), the only MO's that can
be constmcted from $1 and $2 are

Volume 48, Number 8, Augusi 1971 / 495

Obviously 'XI and Ixa correspond to singlet states with
the electrons paired; 3x2 and axa represent substates
of a triplet (total spin fi) with the spin vector parallel,
or antiparallel, to the z axis.
The remaining two determinants (x4 and xs) are
eigenfunctions of S,, with eigenvalue zero, but not of
S2. However we can constmct linear combination of
them that are

It is easily seen that

syax4 = a/&s(8x4) (35)
S.("xr) = 0
S~~X =S SI('xd
) = 0 (36) i
I
Thus 'xs represents a third singlet state, in which the i
electrons are in different RIO's but with paired spins, Figure 1. Contour mop indicating the vmriation of 01 with distances
Ix, y ) of the two electrons along the line AB.
while 3xrrepresents the third substate of the triplet, with
total spin h but with the spin vector perpendicular to
the z axis (so that the component of spin along the of high probability. In this and the other three-di-
z axis is zero). mensional plots shown in this paper the spacing of the
The hydrogen molecule belongs to the D,, point grid lines is in each case 0.1 a.u.
group. Since the AO's $1 and 4%are tolally symmetric Various deductions can be made immediately from
for rotation about the internuclear axis, configurations these diagrams concerning the mode of distribution of
constructed from them must belong to the irreducible the electrons between the two hydrogen atoms. Thus
representations Z,+ or Z,+ (symmetric for rotation the regions of high orbital density in Bz correspond to
about the axis, symmetric (g) or antisymmetric (u) for situations where when electron 1 is near nucleus A,
reflection in the point bisecting the line joining the electron 2 is near nucleus B, and conversely, there is
nuclei). The configurations are classified as very little chance of finding the electrons simultaneously
at the same end of the molecule. This of course is a
follows
consequence of the Pauli exclusion principle; electrons
z.+: 'XI,'xs (37) of the same spin cannot occupy the same point in
Xu+: $x4, 'XI (38) space, so the probability of finding them close together
is also reduced. The singly excited state of 83 cor-
The six configurations are derived from only four responds on the other hand to a "hybrid" of "ionic"
spatial wave functions 81-a structures, H+H- u H-H+; here the electrons are
0, = J . , ~ + I ~ (ground state singlet, 'XI) (39) most likely to be found near the same nucleus. Finally,
in the ground state 81, or in the doubly excited state
Oa, the electrons are as likely to be found near different
nuclei as near the same nucleus; this of course follows
1
0. = - (+,1+34 + #21#,z) (singly excited singlet, 'xs) (41) because in our simple orbital approximation no ac-
v'z count is taken of the tendency of electrons to keep
apart, due to their mutual electrostatic repulsion; the
weighting of "covalent" structures in 02, or "ionic"
These spatial functions can be denoted graphically structures in 83 is due to "exchange" correlation, not
by contour maps in tw.0 dimensions by taking the dis- to electrostatic repulsions.
tances of the electrons along the AB line as the two
coordinates x and y, the contours denoting equal values Energy and Bond Length
of the function 8. Figure 1 shows such a plot for 81. The ground state of H, corresponds to the configura-
Note that there are four points of maximum (and equal) tion 'XI (eqn. (24)). The corresponding electronic
orbital density, corresponding to situations where both energy ExEis given (eqns. (7)-(ll), (Zl), and (22))
electrons are near nucleus A, or both near nucleus B,
or one near nucleus A while the other is near nucleus
B. A better graphical representation is provided
by an analogous plot of P, this indicating the proba-
bility of finding the electrons in various pairs of loca-
tions, and an even better one by a three-dimensional
plot with 0 2 as the z coordinate. Figure 2 represents where the integrations are over the space and spin parts
such plots for the peeks correspond to situations of each spin orbital, and $,a.
Since the wave func-
496 / Journal o f Chemical Education
Figure 2. Three dimensional plot. of 13%versus r and y for o, 8;, b, 8~2e

tion factors into a product of a space part and a

spin part, and since the electronic operator contains no
spin terms, the integral can also be factored

and where ElC is the core energy of an electron oc-

cupying the h4O
Substituting for ~I from eqns. (15) and (16)

+ 2812 [HIP + Hszc + HnC + Hxcl

=- 1
(49)
2
Where
Since the spin functions are orthogonal, the middle
term vanishes; if a and P are normalized, the other
terms are each equal to unity. Hence

Since HIC is a fuiiction of the coordi~atesof electron

1only, and HzCof electron 2 only from symmetry
HIP = H$
HIP = HZIC

Substituting for'HCfrom eqn. (21)

Volume 48, Number 8, August 7 971 / 497

H,,c = S+t(-'/zvta)+,dr (one-center kinetic energy
integral, TI,)

+ +,(-$)+c (one-center nuclear attraction

integral, V d )

S
+ +,(-&)+Id7 (twc-center nuclear attraction
integral, VtzB) (53)
Likewise

= J c$~(-'/nvl')+adr (two-center kinetic energy

integral, TM)
In the last expression, 0.57722 is the approximate value
of an integral while

5 (two-center nuclear attraction

integrslls V d , VIP) (54)

The total electronic energies for the other configura-

All these integrals can be expressed in analytical form, tions (eqns. (25)-(34)) can be found in a precisely similar
using 1s AO's for and (eqn. (13)) way; the derivations are left to the reader
Triplet state, 3 ~ 2 ,
TI, = I/* (55)
Tlr = -'/2[& - 2(1 + TAB)~-~*B] (56)
VllA = -1 (57) where
v,p = -1
rm
+ (I + &)e-"As (58)

v,$ = VIP = -(1 + ns)ecr~n (59)

S = (1 + + i/k~~')e-'~n (60)

Expanding Jl1likewise in terms of AO's and the exchange integral K12is given by

= +
1
4(1 Sd'
[(11,11) + (22,22) + (11,22) +
(22,ll) + (11,12) + (11,21) + (22,12) + Singly excited singlet state, lx6
(22,211 + (12,ll) + (21,ll) + (12,22) +
(21,22) + (12,121 + (21,121 +(lZ,Zl) + (21,Zl)I (61)
where
Doubly excited state, 'xe

From the definition of the integrals where

Also from symmetry

-
(1 - Sl#
[1/2(11,11) + 1/*(11,22)+ (12,12) - 2(11,12)1
(77)
The total energy (ET)of each of these states is given
(eqn. (6)) by adding the internuclear repulsion to the
From eqns. (61)-(64) total electronic energy; in a.u.

Table 1gives values for the basic integrals for various

Electron repulsion integrals (ij,kl) usually have to be values of. rAs, and Table 2 values for the quantities
evaluated by numerical integration; however in this ElC, ESC,Jn, Jlz, K12,and l/mB. Table 3 shows cor-
simple case they can be expressed analytically responding values of the total energy for the various
498 / Journal o f Chemicol Education
 Table 1. Basic Integrals for Hz for Various lnternuclear Distances.
Sn Tn - VnB - VnA (1122)

a All values in ax.

Table 2. Molecular Integrals for Hz for Various lnternuclear Distances.

K12 TAB-'

a All vduelues in a.u

Table 3. Total Energies of Various States of H1at Various
Internuclear Distances*

o All values in a.u.

throughout by the single Slater determinant 'XI. Ex-

pansion of the space part +l'h2
of lx1 (eqn. (24) gives)

Thus the wave function +11+12 can be partitioned into

Figure 3. Plot of total energy af H2 versus i n k r n v d o ~ rdirtonce four equal pafts, corresponding to situations where
( r m l for the ground rtote I1.+I, tripletrtats[%lLtl, singly excited singlet
state ('Z,+l, and doubly excited state I'Z,+l.
both electrons occupy the A 0 61 (i.e., +11+12),or both
+Z (i.e., or where they occupy different AO's
states, while Figure 3 shows a plot of the total energies (+I'&~or +21+~2). This can be seen very clearly fram
versus the internuclear distance. the plots of 01 and el2in Figures 1 and 2a; the general
It will be seen that 'XI does correspond, as we have form of these plots is independent of r * ~ . Obviously
assumed, t o the ground state of H1; the minimum in this cannot be a satisfactory representation because
the curve should correspond to the equilibrium inter- dissociation of H1 must give either (He +
-H) or
nuclear distance and the depth of the line below the (H+ + H-), not a "hybrid" of the two. Note that
limit (HA + He) to the boncl energy. The values dissociation of the triplet 3&+, and of the singly ex-
cited singlet '&+,is correctly predicted to give a "pure"
estimated in this way (0.84 A,-2.65 eV) are in fair
agreement with experiment (0.74A, 4.74 eV). state (H. + +
.H) or (H+ H-), while dissociation of
The curve for the singly excited state (%+) also has the doubly excited state again gives a hybrid. The
a minimum, implying that it should be a bound state; reason for this difference will appear presently.
Hz has an absorption hand a t 109 nm corresponding to The total energy (ET) of Hz can he written (eqns.
the transition (I&+ -+'2,+). The observed excitation (45)-(71)) in the form
energy (11.4 eV) for the zero-zero transition is in good
agreement with that estimated from Figure 1 (13.2 eV).
The other two states have no minima and so correspond
t o dissociation into hydrogen atoms.
It will be noticed that the curve for the ground state
does not converge t o the correct limit (HA HB) for +
large ~ A B ; this is because we have represented the system
Volume 48, Number 8, August 1971 / 499
 leads t o two states whose energies (Em)are the roots of
the secular equation

The corresponding coefficients A,, (eqn. (81)) are given

+ Hr,A,a
( H I , - Em)Am1 = 0 (83)
Here

where El" is the total electronic energy of the configura-

tion 'XI; likewise
HOB= E,B (85)
Also

The numerator of the first term (A) represents the

(constant) energy of two hydrogen atoms; A increases
with decreasing r * ~due to crowding of the electrons.
The second term (B) in eqn. (80) represents the mutual
interaction of the two atoms, due t o classical electro-
static forces; this term does show an energy minimum
with decreasing rAs. Figure 4 shows a plot of A, B,
and ( A + B) versus r*.; the composite curve shows The first two integrals vanish because GI and J.2 are
no minimum whatsoever. These terms collectively orthogonal while the third is equal to Kls (eqn. (74)).
represent the situation that would hold if the electron Using the expressions for ElEand EnEabove, and the
distribution (h)= of the occupied A40 in Hz were a integrals from Tables 1 and 2, one can calculate the
simple superposition [(+I)= +(+z)2] of those for the energies of the two states (8. and 0,) resulting from
component AO's. I n fact there is an additional term mixing of 'xl and 'xs and also the coefficients A, and
2 , corresponding t o the interference of electron As (eqn. (83)). Figure 5 shows plots of the total en-
waves when the atoms approach; the last term (C) in ergies of e., O,, '~6, and the triplet state versus r * ~ .
eqn. (80) represents the corresponding correction to the Note that the g state x, now correctly dissociates into
+ +
"classical" energy. The plots of C, and (A B C), (H + .H), while the doubly excited state, like the
in Figure 4 show that this nonclassical term accounts
for the whole of the binding in Hz. This is a special
singly excited one, now dissociates into (H+ + H-).
The minimumin the ground state case leads to esti-
case of a general result; chemical binding, in an orbital mates of 0.88 A and 3.23 eV for the equilibrium bond
description, arises mainly from terms involving one- length and bond energy. The calculated excitation
electron resonance integrals. energy remains almost unchanged (13.6 eV).
Configuration Inlerachn
Allowance for electron correlation can be introduced
into the SCF treatment of a molecule by writing the
wave function (3 as a linear combination of configura-
tions x, derived by dist,rihuting the electrons various
possible ways among the various MO's

If the molecule has symmetry, the wave function must

have corresponding symmetry; 0 must then be written
as a combination of configurations X, that behave in
the same way under the symmetry operation in ques-
tion. I n the case of Hz, only configurations which are
either all gerade (g), or all ungerade (u), can mix, and
they must also have similar multiplicities in order that
e can represent a r e d spin state. Of our four configura-
for Hz, 'XI and 'xs can mix, being both '2,; the other
two configurations are both Z,, and they cannot mix
with one another since they are of different multiplicity.
This configuration interaction between 'XI and 'xs
500 / Journal of Chemical Educafion
 Figure 6 shows how the total electron density varies
with internuclear separation for the ground state €I.,
using the formalism of Figure 2. Note that the
"peaks" corresponding t o "ionic" states are now lower
than those for the "covalent" ones, even at equilib-
rium, and disappear with increasing r * ~ .
Literature Cited
(1) Accountsdthe LCAO SCF MO &had: (a) Dnumb, R., L ~ r s s v mR., .
AND MOBER,C., "Quantum Chemistry." Interscience Publishers,
Ino.. New Yark, 1959. (b) SALEM,L., "The Molecular OrbitalTheory
of Conjugated Syatema." W. A. Benjsmin Ino., New York, 1966.
(4 DEVAR.M. J. S., "The Moleoulsr Orbital Theory of Organic
Chemistrv." MoGraw-Hill Book Co.. Inc.. New York. 1969. Id1
POPLE.J.-A,, AND BEYEBIO(IE, D. L., " ~ p p r ( l . i m & eMoleoulhr o r b &
Theory," McGrhw-Hill Book Co.. Ino.. New York. 1970.
(2) Hydiwcn nolecvlor calrulolrons: For a recent paper and a detailed
bibl~ogr&phy,see MOLB*N. A. D.. W ~ r s s ,A,. m n Y o s ~ m z r s e ,M., A
Rou. Mad. Phys., 32, 25 (1960). The simple MO treatment given
here was first published by Comsow. C. A,, Trans. Foroday SOE..33, Figwe 6. Electron density functions for the gmund state B.: 0, for r ~ =
s
1479 (1937). 1.4 a".;b,forme = 3 0.u.; c , f o r r m = 5 O.Y.

Volume 48, Number 8, August 1971 / 501