Hartree-Fock Method

http://www.chm.davidson.edu/ronutt/che401/HartreeFock/HartreeFock.htm

Hartree-Fock Method
Consider a molecule with an electron configuration in which the 2N electrons are paired, e.g. H2O : (1a1 )2 (2a1 )2 (1b2 )2 (3a1 )2 (1b1 )2. Such a configuration is called a closed-shell configuration. The electronic state of the molecule is approximated by the wavefunction Y. Y is the Slater determinant of one-electron spin orbitals (eq 1). Spin orbitals have a space part f and a spin part a or b.

In this case the orbitals f are molecular orbitals and form an orthonormal set.

The expectation value for the energy, expressed in atomic units , is

For a closed-shell configuration eq 3 reduces to the form

where Hii is the average kinetic energy and the potential energy for the electrostatic attraction between the nuclei and the electron in fi,

Jij called the Coulomb integral is the potential energy for the electrostatic repulsion between the electron with the electron density function (fi )2 and the electron with the electron density function (fj )2,

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Hartree-Fock Method

http://www.chm.davidson.edu/ronutt/che401/HartreeFock/HartreeFock.htm

and Kij called the exchange integral arises from the requirement that Y be antisymmetric with respect to the permutation of the coordinates of any two electrons.

Given any set of molecular orbitals f that satisfy the boundary conditions of the problem and eq 2, the E calculated in eq 3 will always be greater than the true ground state energy. Therefore, we wish to find the set of molecular orbitals that minimizes the value of E. Since variations in the molecular orbitals, df, at the minimum and since is stationary with respect to small must remain constant with a small df,

then "Lagrange's method of undetermined multipliers" may be used to derive the expression1

ei is the Lagrangian multiplier , and

is the Fock operator

where

is the Coulomb operator

and

is the exchange operator defined with respect to the orbital upon which it operates

Let fi be approximated by a linear combination of basis functions cy.

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Hartree-Fock Method

http://www.chm.davidson.edu/ronutt/che401/HartreeFock/HartreeFock.htm

The basis functions are one-electron orbitals such as atomic orbitals located on the nuclei, b is the number of basis functions, and the coefficients cyi are constants. Substituting eq 12 into eq 8 gives

where the Coulomb and exchange operators in eq 13 are

If eq 13 is multiplied by cz and integrated over all space, then

Let Fzy and Szy represent the intregrals in eq 14

and rearrange eq 14 to obtain

Eq 15 is called a secular equation, and there are b such equations, one for each value of z from 1 to b. To obtain a nontrivial solution to eq 15, i.e. a solution for which the values of the coefficients cyi are not zero, the determinant of the terms inside the parentheses in eq 15 must be equal to zero.

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Hartree-Fock Method

http://www.chm.davidson.edu/ronutt/che401/HartreeFock/HartreeFock.htm

The determinant in eq 16 is called the secular determinant.2 How then do we find the set of molecular orbitals f that minimizes the value of E? We begin with the selection of a set of basis functions cy and a set of guesses for the initial values of the coefficients cyi. These cy's and initial values of cyi are used to calculate the Coulomb and exchange operators and finally the Fock operator (eq 13). Next, the elements Fzy and Szy in the secular equation (eq 15) are calculated, and the determinantal equation (eq 16) is solved to obtain a set of values for the ei's. These values for the ei's are substituted into the secular equation (eq 15), and a new set of values for the coefficents cyi are computed. The new values for the cyi's are used to construct a new Fock operator (eq 13) which is used to compute new Fzy and Szy elements. The new elements are substituted into the determinantal equation (eq 16), and it is solved to obtain a new set of values for the ei's. The new ei values are substituted into the secular equation (eq 15), and an improved set of values for coefficients cyi is found. This iterative process is continued until the variations in the values of the ei's and the cyi's from one cycle to the next fall below an arbitrary threshold. At this point the process has converged, and the resulting values for the cyi's are used to obtain the f's (eq 12) that minimize the value of E. Since these f's are nearly identical to the orbitals used to calculate the Coulomb and exchange operators (eq 13) in the last cycle, they are said to be self-consistent orbitals, and the process is called the self-consistent-field (SCF) method.2,3 The Lagrangian multiplier ei is called the orbital energy and includes the kinetic energy of the electron in molecular orbital fi plus the energies resulting from the interactions of the electron with the nuclei and the other 2N-1 electrons. The total electronic energy is

The Coulomb and exchange integrals are included in eq 17 because the energies associated with the interactions between the electrons are counted twice in the summation of orbital energies. The Coulomb and exchange energies due to the interactions between electrons 1 and 2 are included in the orbital energy for electron 1 and again in the orbital energy for electron 2. The internuclear repulsion energy (eq 18) for a specific molecular geometry

is add to the total electronic energy to obtain the Hartree-Fock energy, EHF.1,2

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Hartree-Fock Method

http://www.chm.davidson.edu/ronutt/che401/HartreeFock/HartreeFock.htm

1) Lowe, John P. Quantum Chemistry; Academic Press: New York, 1978; pp 509-519. 2) Levine, Ira N. Quantum Chemistry, 5th ed.; Prentice Hall : Upper Saddle River, 2000; pp 426-442. 3) Richards, W. G.; Horsley, J. A. Ab Initio Molecular Calculations for Chemists; Oxford University Press: London, 1970; pp 1-40.

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