TY - JOUR
T1 - Analytic Gradients for Selected Configuration Interaction
AU - Coe, Jeremy P.
N1 - Funding Information:
J.P.C. thanks the Engineering and Physical Sciences Research Council UK (EPSRC) for support via EP/V006746.
Publisher Copyright:
© 2023 The Author. Published by American Chemical Society.
PY - 2023/2/14
Y1 - 2023/2/14
N2 - We develop analytic gradients for selected configuration interaction wave functions. Despite all pairs of molecular orbitals now potentially having to be considered for the coupled perturbed Hartree-Fock equations, we show that degenerate orbital pairs belonging to different irreducible representations in the largest abelian subgroup do not need to be included and instabilities due to degeneracies are avoided. We introduce seminumerical gradients and use them to validate the analytic approach even when near degeneracies are present due to high-symmetry geometries being slightly distorted to break symmetry. The method is applied to carbon monoxide, ammonia, square planar H
4, hexagonal planar H
6, and methane for a range of bond lengths where we demonstrate that analytic gradients for selected configuration interaction can approach the quality of full configuration interaction yet only use a very small fraction of its determinants.
AB - We develop analytic gradients for selected configuration interaction wave functions. Despite all pairs of molecular orbitals now potentially having to be considered for the coupled perturbed Hartree-Fock equations, we show that degenerate orbital pairs belonging to different irreducible representations in the largest abelian subgroup do not need to be included and instabilities due to degeneracies are avoided. We introduce seminumerical gradients and use them to validate the analytic approach even when near degeneracies are present due to high-symmetry geometries being slightly distorted to break symmetry. The method is applied to carbon monoxide, ammonia, square planar H
4, hexagonal planar H
6, and methane for a range of bond lengths where we demonstrate that analytic gradients for selected configuration interaction can approach the quality of full configuration interaction yet only use a very small fraction of its determinants.
UR - http://www.scopus.com/inward/record.url?scp=85146608578&partnerID=8YFLogxK
U2 - 10.1021/acs.jctc.2c01062
DO - 10.1021/acs.jctc.2c01062
M3 - Article
C2 - 36656261
SN - 1549-9618
VL - 19
SP - 874
EP - 886
JO - Journal of Chemical Theory and Computation
JF - Journal of Chemical Theory and Computation
IS - 3
ER -