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Chapter 18

Chapter 18

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Chapter 18
The single Slater determinant wavefunction (properly spin and symmetry adapted) is the
starting point of the most common mean field potential. It is also the origin of the molecular
orbital concept.
I. Optimization of the Energy for a Multiconfiguration Wavefunction
A. The Energy Expression

The most straightforward way to introduce the concept of optimal molecular orbitals is to consider a trial wavefunction of the form which was introduced earlier in Chapter 9.II. The expectation value of the Hamiltonian for a wavefunction of the multiconfigurational

form
\u03a8= \u03a3ICI\u03a6I,
where\u03a6I is a space- and spin-adapted CSF which consists of determinental wavefunctions
|\u03c6I1\u03c6I2\u03c6I3. . .\u03c6IN| , can be written as:
E =\u03a3I,J = 1, M CICJ <\u03a6I | H |\u03a6J > .
The spin- and space-symmetry of the\u03a6I determine the symmetry of the state\u03a8 whose
energy is to be optimized.

In this form, it is clear that E is a quadratic function of the CI amplitudes CJ ; it is a quartic functional of the spin-orbitals because the Slater-Condon rules express each <\u03a6I | H |\u03a6J > CI matrix element in terms of one- and two-electron integrals <\u03c6i | f |\u03c6j > and <\u03c6i \u03c6j | g |\u03c6k\u03c6l > over these spin-orbitals.

B. Application of the Variational Method
The variational method can be used to optimize the above expectation value
expression for the electronic energy (i.e., to make the functional stationary) as a function of
the CI coefficients CJ and the LCAO-MO coefficients {C\u03bd,i} that characterize the spin-

orbitals. However, in doing so the set of {C\u03bd,i} can not be treated as entirely independent variables. The fact that the spin-orbitals {\u03c6i} are assumed to be orthonormal imposes a set of constraints on the {C\u03bd,i}:

<\u03c6i |\u03c6j> =\u03b4i,j =\u03a3\u00b5,\u03bd C*\u00b5,i <\u03c7\u00b5|\u03c7\u03bd > C\u03bd,j.

These constraints can be enforced within the variational optimization of the energy function
mentioned above by introducing a set of Lagrange multipliers {\u03b5i,j } , one for each
constraint condition, and subsequently differentiating

E -\u03a3i,j \u03b5i,j [\u03b4i,j -\u03a3\u00b5,\u03bd C*\u00b5,i <\u03c7\u00b5|\u03c7\u03bd > C\u03bd,j ]
with respect to each of the C\u03bd,i variables.
C. The Fock and Secular Equations

Upon doing so, the following set of equations is obtained (early references to the derivation of such equations include A. C. Wahl, J. Chem. Phys. 41 ,2600 (1964) and F. Grein and T. C. Chang, Chem. Phys. Lett. 12, 44 (1971); a more recent overview is

presented in R. Shepard, p 63, in Adv. in Chem. Phys. LXIX, K. P. Lawley, Ed., Wiley-

Interscience, New York (1987); the subject is also treated in the textbook Second Quantization Based Methods in Quantum Chemistry, P. J\u00f8rgensen and J. Simons, Academic Press, New York (1981))) :

\u03a3J =1, MHI,JCJ= E CI ,I = 1, 2, ... M, and
F\u03c6i =\u03a3j \u03b5i,j \u03c6j,
where the\u03b5i,j are Lagrange multipliers.

The first set of equations govern the {CJ} amplitudes and are called the CI- secular
equations. The second set determine the LCAO-MO coefficients of the spin-orbitals {\u03c6j}
and are called the Fock equations. The Fock operator F is given in terms of the one- and
two-electron operators in H itself as well as the so-called one- and two-electron density
matrices\u03b3i,j and\u0393i,j,k,l which are defined below. These density matrices reflect the
averaged occupancies of the various spin orbitals in the CSFs of\u03a8. The resultant

expression for F is:
F\u03c6i =\u03a3j \u03b3i,j h\u03c6j +\u03a3j,k,l \u0393i,j,k,l Jj,l\u03c6k ,
where h is the one-electron component of the Hamiltonian (i.e., the kinetic energy operator
and the sum of coulombic attractions to the nuclei). The operator Jj,l is defined by:
Jj,l\u03c6k(r) =\u2321\u2320 \u03c6*j(r')\u03c6l(r')1/|r-r'| d\u03c4'\u03c6k(r),

where the integration denoted d\u03c4' is over the spatial and spin coordinates. The so-called
spin integration simply means that the\u03b1 or\u03b2 spin function associated with\u03c6l must be the
same as the\u03b1 or\u03b2 spin function associated with\u03c6j or the integral will vanish. This is a

consequence of the orthonormality conditions <\u03b1|\u03b1> = <\u03b2|\u03b2> = 1, <\u03b1|\u03b2> = <\u03b2|\u03b1> = 0.
D. One- and Two- Electron Density Matrices
The density matrices introduced above can most straightforwardly be expressed in
terms of the CI amplitudes and the nature of the orbital occupancies in the CSFs of\u03a8 as
follows:
1.\u03b3i,i is the sum over all CSFs, in which\u03c6i is occupied, of the square of the CI coefficient
of that CSF:
\u03b3i,i=\u03a3I(with \u03c6i occupied) C2I.
2.\u03b3i,j is the sum over pairs of CSFs which differ by a single spin-orbital occupancy (i.e.,

one having\u03c6i occupied where the other has\u03c6j occupied after the two are placed into maximal coincidence-the sign factor (sign) arising from bringing the two to maximal coincidence is attached to the final density matrix element):

\u03b3i,j= \u03a3I,J (sign)( with \u03c6i occupied in I where \u03c6j is in J) CICJ.
The two-electron density matrix elements are given in similar fashion:
3.
\u0393i,j,i,j= \u03a3I (with both \u03c6iand \u03c6j occupied) CICI;
4.
\u0393i,j,j,i= -\u03a3I (with both \u03c6iand \u03c6j occupied) CICI= -\u0393i,j,i,j

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