Configuration-interaction energy derivatives in a fully variational formulation

Abstract

A configuration-interaction energy function (Lagrange) which is variational in all variables, including the orbital rotational parameters, is constructed. When this Lagrangian is used for obtaining configuration-interaction derivatives, all the important simplifications which occur for derivatives of variational wave functions carry over in a straightforward way. In particular, the state and orbital rotational response parameters obey the 2n+1 rule and the Lagrange multipliers obey the somewhat stronger 2n+2 rule. The simplifications which are normally obtained by invoking the Handy-Schaefer technique are automatically incorporated to all orders. Simple expressions for energy derivatives up to third order are presented. The relationship between the numerical errors in the variational parameters and the errors in the calculated energy derivatives is discussed.