Analytic energy gradients for variational two-electron reduced-density matrix methods within the density-fitting approximation

TL;DR

This paper develops and applies analytic energy gradients for v2RDM-CASSCF with density-fitting, enabling efficient geometry optimizations of large molecules and assessing the method's accuracy against traditional approaches.

Contribution

It introduces a density-fitting implementation of analytic energy gradients for v2RDM-CASSCF, allowing larger system studies and detailed comparison with CI-CASSCF results.

Findings

Density-fitting reduces computational cost significantly.

v2RDM-CASSCF geometries agree closely with CI-CASSCF when including partial three-particle conditions.

The method successfully optimized geometries for large acenes up to C50H28.

Abstract

Analytic energy gradients are presented for a variational two-electron reduced-density-matrix-driven complete active space self-consistent field (v2RDM-CASSCF) procedure that employs the density-fitting (DF) approximation to the two-electron repulsion integrals. The DF approximation significantly reduces the computational cost of v2RDM-CASSCF gradient evaluation, in terms of both the number of floating-point operations and memory requirements, enabling geometry optimizations on much larger chemical systems than could previously be considered at the this level of theory [E. Maradzike et al., J. Chem. Theory Comput., 2017, 13, 4113-4122]. The efficacy of v2RDM-CASSCF for computing equilibrium geometries and harmonic vibrational frequencies is assessed using a set of 25 small closed- and open-shell molecules. Equilibrium bond lengths from v2RDM-CASSCF differ from those obtained from configuration-interaction-driven CASSCF (CI-CASSCF) by 0.62 pm and 0.05 pm, depending on whether the optimal reduced-density matrices from v2RDM-CASSCF satisfy two-particle N-representability conditions (PQG) or PQG plus partial three-particle conditions (PQG+T2), respectively. Harmonic vibrational frequencies, which are obtained by finite differences of v2RDM-CASSCF analytic energy gradients, similarly demonstrate that quantitative agreement between v2RDM- and CI-CASSCF requires the consideration of partial three-particle N-representability conditions. Lastly, optimized geometries are obtained for the lowest-energy singlet and triplet states of the linear polyacene series up to dodecacene (C50H28), in which case the active space is comprised of 50 electrons in 50 orbitals. The v2RDM-CASSCF singlet-triplet energy gap extrapolated to an infinitely-long linear acene molecule is found to be 7.8 kcal/mol