Magnetic Properties of Single-Molecule Magnets Derived from Equation-of-Motion Coupled-Cluster Wave Functions
ORAL
Abstract
This work presents validation studies for magnetic properties of transition metal complexes that are proposed as single-molecule magnets (SMMs).
We obtain zero-order states from non-relativistic equation-of-motion coupled-cluster (EOM-CC) calculations. The effects of spin-orbit coupling and magnetic field are treated perturbatively by using the Breit-Pauli Hamiltonian and the Zeeman operator, respectively. We compute magnetization and susceptibility through Boltzmann distribution law and numerical differentiation of the partition function. To compare with experiments on powder samples, we numerically average these quantities over a large set of field orientations.
Our protocol is applied to mononuclear Fe(II), Fe(I), and Co(II) SMMs in different coordination environments, such as trigonal pyramidal, tetrahedral, and linear. To obtain spin-free states, we use different flavors of the EOM-CC method, e.g. the ionization (EOM-IP), electron-attached (EOM-EA), and spin-flip (EOM-SF) variants. The computed energy barriers for spin inversion, and magnetization and susceptibility data are in close agreement with experiment.
The presented results provide evidence for our computational strategy being a robust and accurate tool for describing magnetic anisotropy of mononuclear SMMs.
We obtain zero-order states from non-relativistic equation-of-motion coupled-cluster (EOM-CC) calculations. The effects of spin-orbit coupling and magnetic field are treated perturbatively by using the Breit-Pauli Hamiltonian and the Zeeman operator, respectively. We compute magnetization and susceptibility through Boltzmann distribution law and numerical differentiation of the partition function. To compare with experiments on powder samples, we numerically average these quantities over a large set of field orientations.
Our protocol is applied to mononuclear Fe(II), Fe(I), and Co(II) SMMs in different coordination environments, such as trigonal pyramidal, tetrahedral, and linear. To obtain spin-free states, we use different flavors of the EOM-CC method, e.g. the ionization (EOM-IP), electron-attached (EOM-EA), and spin-flip (EOM-SF) variants. The computed energy barriers for spin inversion, and magnetization and susceptibility data are in close agreement with experiment.
The presented results provide evidence for our computational strategy being a robust and accurate tool for describing magnetic anisotropy of mononuclear SMMs.
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Presenters
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Maristella Alessio
Department of Chemistry, University of Southern California
Authors
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Maristella Alessio
Department of Chemistry, University of Southern California
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Anna Krylov
Univ of Southern California, Department of Chemistry, University of Southern California