Zero-Field Splitting Calculations by Multiconfiguration Pair-Density Functional Theory

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Zero-field splitting (ZFS) is a fundamental molecular property that is especially relevant for single-molecule magnets (SMMs), electron paramagnetic resonance spectra, and quantum computing. Developing a method that can accurately predict ZFS parameters can be very powerful for designing new SMMs. One of the challenges is to include external correlation in an inherently multiconfigurational open-shell species for the accurate prediction of magnetic properties. Previously available methods depend on expensive multireference perturbation theory calculations to include external correlation. In this paper, we present spin-orbit-inclusive multiconfiguration and multistate pair-density functional theory (MC-PDFT) calculations of ZFSs; these calculations have a cost comparable to complete-active-space self-consistent field (CASSCF) theory, but they include correlation external to the active space. We found that combining a multistate formulation of MC-PDFT, namely, compressed-state multistate pair-density functional theory, with orbitals optimized by weighted-state-averaged CASSCF, yields reasonably accurate ZFS results.

Original languageEnglish (US)
Pages (from-to)2199-2207
Number of pages9
JournalJournal of Chemical Theory and Computation
Issue number4
StatePublished - Apr 12 2022

Bibliographical note

Funding Information:
The locally modified version of Gaussian 16, Revision C.0.1, was created and compiled by Siriluk Kanchanakungwankul. The present work was supported in part by the Air Force Office of Scientific Research by grant no. FA9550-11-0078.

Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.


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