Spin-Pure Stochastic-CASSCF via GUGA-FCIQMC Applied to Iron-Sulfur Clusters.


Type
Article
Change log
Authors
Weser, Oskar 
Bogdanov, Nikolay A  ORCID logo  https://orcid.org/0000-0002-5437-4919
Alavi, Ali 
Abstract

In this work, we demonstrate how to efficiently compute the one- and two-body reduced density matrices within the spin-adapted full configuration interaction quantum Monte Carlo (FCIQMC) method, which is based on the graphical unitary group approach (GUGA). This allows us to use GUGA-FCIQMC as a spin-pure configuration interaction (CI) eigensolver within the complete active space self-consistent field (CASSCF) procedure and hence to stochastically treat active spaces far larger than conventional CI solvers while variationally relaxing orbitals for specific spin-pure states. We apply the method to investigate the spin ladder in iron-sulfur dimer and tetramer model systems. We demonstrate the importance of the orbital relaxation by comparing the Heisenberg model magnetic coupling parameters from the CASSCF procedure to those from a CI-only (CASCI) procedure based on restricted open-shell Hartree-Fock orbitals. We show that the orbital relaxation differentially stabilizes the lower-spin states, thus enlarging the coupling parameters with respect to the values predicted by ignoring orbital relaxation effects. Moreover, we find that, while CASCI results are well fit by a simple bilinear Heisenberg Hamiltonian, the CASSCF eigenvalues exhibit deviations that necessitate the inclusion of biquadratic terms in the model Hamiltonian.

Description

Funder: Max-Planck-Gesellschaft

Keywords
34 Chemical Sciences, 3406 Physical Chemistry
Journal Title
J Chem Theory Comput
Conference Name
Journal ISSN
1549-9618
1549-9626
Volume Title
17
Publisher
American Chemical Society (ACS)
Sponsorship
H2020 Research Infrastructures (952165)