The all configuration mean energy multiconfiguration self-consistent-field method. I. Equal configuration weights

ABSTRACT

The All Configuration Mean Energy (ACME) conditions are a special case of state averaging for Multiconfigurational Self-Consistent-Field (MCSCF) orbital optimisation. The method is formulated using the Graphical Unitary Group Approach (GUGA) in which the Configuration State Function (CSF) basis is represented as walks within a Shavitt graph. This graphical formulation leads to efficient recursive algorithms for the energy and reduced density matrices (RDM) that are independent of the CSF dimension and that scale only as O(n²) where n is the number of occupied orbitals. The Hamiltonian matrix diagonalization step is obviated and the CSF expansion coefficients are neither referenced nor required during the orbital optimisation. This allows MCSCF orbital optimisation to be performed for essentially unlimited numbers of active orbitals and arbitrarily large CSF expansions. The discussion includes various types of CSF expansion spaces, the partitioning of the essential and redundant orbital optimisation parameters, the computation of the spin-density, and the formulation of state-specific analytic gradients and nonadiabatic coupling for high-level electronic structure methods that use the ACME MCSCF orbitals.

GRAPHICAL ABSTRACT

KEYWORDS:

• MCSCF
• Electronic Structure
• State Averaging
• Analytic Gradient
• Nonadiabatic Coupling

Disclosure statement

No potential conflict of interest was reported by the authors.

Additional information

Funding

This work was supported by the Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, U.S. Department of Energy, under contract DE-AC02-06CH11357.