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

Overview

Journal J Chem Theory Comput

Publisher American Chemical Society

Specialties Biochemistry
Chemistry

Date 2021 Sep 1

PMID 34469685

Citations 13

Authors

Werner Dobrautz

Oskar Weser

Nikolay A Bogdanov

Ali Alavi

Giovanni Li Manni

Affiliations

Soon will be listed here.

Abstract

In this work, we demonstrate how to efficiently compute the one- and two-body reduced density matrices within the 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.

Citing Articles

Effective Hamiltonians from Spin-Adapted Configuration Interaction.

Safari A, Bogdanov N J Chem Theory Comput. 2025; 21(2):539-548.

PMID: 39778153 PMC: 11780745. DOI: 10.1021/acs.jctc.4c01380.

Restricted Open-Shell Hartree-Fock Method for a General Configuration State Function Featuring Arbitrarily Complex Spin-Couplings.

Leyser da Costa Gouveia T, Maganas D, Neese F J Phys Chem A. 2024; 128(25):5041-5053.

PMID: 38886177 PMC: 11215774. DOI: 10.1021/acs.jpca.4c00688.

Toward Real Chemical Accuracy on Current Quantum Hardware Through the Transcorrelated Method.

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PMID: 38723159 PMC: 11137825. DOI: 10.1021/acs.jctc.4c00070.

Distributed Implementation of Full Configuration Interaction for One Trillion Determinants.

Gao H, Imamura S, Kasagi A, Yoshida E J Chem Theory Comput. 2024; 20(3):1185-1192.

PMID: 38314701 PMC: 10867839. DOI: 10.1021/acs.jctc.3c01190.

Toward a Stochastic Complete Active Space Second-Order Perturbation Theory.

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