Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 17, Issue 7, Pages 4225-4241Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.1c00430
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Funding
- Department of Energy [DE-SC0018910]
- U.S. Department of Energy (DOE) [DE-SC0018910] Funding Source: U.S. Department of Energy (DOE)
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The study introduces a new computational protocol for calculating the macroscopic magnetic properties of transition-metal complexes, demonstrating excellent performance in describing magnetic behavior and explaining trends in magnetic anisotropy and spin-reversal energy barriers.
We present a new computational protocol for computing macroscopic magnetic properties of transition-metal complexes using the equation-of-motion coupled-cluster (EOM-CC) framework. The approach follows a two-step state-interaction scheme: we first compute zero-order states using nonrelativistic EOM-CC and then use these states to evaluate matrix elements of the spin-orbit and Zeeman operators. Diagonalization of the resulting Hamiltonian yields spin-orbit- and field-perturbed eigenstates. Temperature- and field-dependent magnetization and susceptibility are computed by numerical differentiation of the partition function. To compare with powder-sample experiments, these quantities are numerically averaged over field orientations. We applied this protocol to several single-molecule magnets (SMMs) with Fe(II) and Fe(III) in trigonal pyramidal, linear, and trigonal bipyramidal coordination environments. We described the underlying electronic structure by the electron-attachment (EOM-EA) and spin-flip (EOM-SF) variants of EOM-CC. The computed energy barriers for spin inversion, and macroscopic magnetization and susceptibility agree well with experimental data. Trends in magnetic anisotropy and spin-reversal energy barriers are explained in terms of a molecular orbital picture rigorously distilled from spinless transition density matrices between many-body states. The results illustrate excellent performances of EOM-CC in describing magnetic behavior of mononuclear transition-metal SMMs.
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