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

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [1];  [1];  [2];  [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)
  2. Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
+ Show Author Affiliations
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
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
Air Force Office of Scientific Research (AFOSR); Air Force Research Laboratory (AFRL); USDOE
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1875663
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 4 Vol. 18; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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