Spin Purification in Full-CI Quantum Monte Carlo via a First-Order Penalty Approach.
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Publication Date
2022-03-31Journal Title
J Phys Chem A
ISSN
1089-5639
Publisher
American Chemical Society (ACS)
Volume
126
Issue
12
Pages
2050-2060
Language
eng
Type
Article
This Version
VoR
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Weser, O., Liebermann, N., Kats, D., Alavi, A., & Li Manni, G. (2022). Spin Purification in Full-CI Quantum Monte Carlo via a First-Order Penalty Approach.. J Phys Chem A, 126 (12), 2050-2060. https://doi.org/10.1021/acs.jpca.2c01338
Abstract
In this article, we demonstrate that a first-order spin penalty scheme can be efficiently applied to the Slater determinant based Full-CI Quantum Monte Carlo (FCIQMC) algorithm, as a practical route toward spin purification. Two crucial applications are presented to demonstrate the validity and robustness of this scheme: the 1Δg ← 3Σg vertical excitation in O2 and key spin gaps in a [Mn3(IV)O4] cluster. In the absence of a robust spin adaptation/purification technique, both applications would be unattainable by Slater determinant based ground state methods, with any starting wave function collapsing into the higher-spin ground state during the optimization. This strategy can be coupled to other algorithms that use the Slater determinant based FCIQMC algorithm as configuration interaction eigensolver, including the Stochastic Generalized Active Space, the similarity-transformed FCIQMC, the tailored-CC, and second-order perturbation theory approaches. Moreover, in contrast to the GUGA-FCIQMC technique, this strategy features both spin projection and total spin adaptation, making it appealing when solving anisotropic Hamiltonians. It also provides spin-resolved reduced density matrices, important for the investigation of spin-dependent properties in polynuclear transition metal clusters, such as the hyperfine-coupling constants.
Identifiers
35298155, PMC8978180
External DOI: https://doi.org/10.1021/acs.jpca.2c01338
This record's URL: https://www.repository.cam.ac.uk/handle/1810/336159
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