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Variational principle

Putting everything together, we now have our expression for the total energy,

  eqnarray125

where tex2html_wrap_inline667 is some known function, tex2html_wrap_inline673 is the potential energy field created by the nuclei, tex2html_wrap_inline675 is the simple electron static interaction among the nuclei,

displaymath677

and tex2html_wrap_inline661 (usually equal to two) is the number of electrons in orbital i. Note that the expression (12) maps each possible choice of the set of electronic orbitals tex2html_wrap_inline683 to a unique value for the energy of the system and thereby gives the total energy E as a function of the orbital functions tex2html_wrap_inline687 . Such an expression which returns a number as a function of other functions is called a functional and denoted with square brackets as we do in Eq. (12).

We now have a functional for the energy in terms of the orbitals, but which orbitals are the right ones to use? The answer is quite sensible: the correct orbitals are those which minimize the total energy E in (12) while obeying the orthonormality constraints (6). Combined with this variational principle, Eq. (12) now gives a complete prescription for computing total energies, and thereby all of the properties mentioned in Sec. 2.



Tomas Arias
Tue Feb 8 12:49:58 EST 2000