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

Journal Article · · Molecular Physics
 [1];  [1]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
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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. 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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1543139
Journal Information:
Molecular Physics, Vol. 117, Issue 17; ISSN 0026-8976
Publisher:
Taylor & FrancisCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

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Cited By (1)

Representations of Shavitt Graphs Within the Graphical Unitary Group Approach journal October 2019

Figures / Tables (7)

Table 1(p. 39)table Table 1
Table 2(p. 40)table Table 2
Table 3(p. 40)table Table 3
Figure 1(p. 41)figure Figure 1
Figure 2(p. 41)figure Figure 2
Figure 3(p. 42)figure Figure 3
Figure 4(p. 43)figure Figure 4

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
MCSCF
analytic gradient
electronic structure
nonadiabatic coupling
state averaging