Zero-Field Splitting Calculations by Multiconfiguration Pair-Density Functional Theory
- 23 March 2022
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of Chemical Theory and Computation
- Vol. 18 (4) , 2199-2207
Abstract
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.Keywords
Funding Information
- Air Force Office of Scientific Research (FA9550110078)
This publication has 56 references indexed in Scilit:
- Theoretical Determination of the Zero-Field Splitting in Copper Acetate MonohydrateInorganic Chemistry, 2011
- Systematic Theoretical Study of the Zero-Field Splitting in Coordination Complexes of Mn(III). Density Functional Theory versus Multireference Wave Function ApproachesThe Journal of Physical Chemistry A, 2010
- Calculation of the zero-field splitting tensor on the basis of hybrid density functional and Hartree-Fock theoryThe Journal of Chemical Physics, 2007
- First-principle computation of zero-field splittings: Application to a high valent Fe(IV)-oxo model of nonheme iron proteinsThe Journal of Chemical Physics, 2005
- Pseudooctahedral Complexes of Vanadium(III): Electronic Structure Investigation by Magnetic and Electronic SpectroscopyInorganic Chemistry, 2004
- High-Frequency and -Field EPR Spectroscopy of Tris(2,4-pentanedionato)manganese(III): Investigation of Solid-State versus Solution Jahn−Teller EffectsInorganic Chemistry, 2003
- Magnetic anisotropy barrier for spin tunneling inmoleculesPhysical Review B, 1999
- Second-order perturbation theory with a complete active space self-consistent field reference functionThe Journal of Chemical Physics, 1992
- Electron paramagnetic resonance spectra of molybdenum(III) complexes: direct observation of molybdenum-95 hyperfine interaction and implications for molybdoenzymesInorganic Chemistry, 1980
- Paramagnetic anisotropies and zero-field splitting of some high-spin iron(III) complexesJournal of the Chemical Society A: Inorganic, Physical, Theoretical, 1969