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J Chem Theory Comput. 2015 Sep 8;11(9):4169-81. doi: 10.1021/acs.jctc.5b00535. Epub 2015 Aug 14.

Current Density Functional Theory Using Meta-Generalized Gradient Exchange-Correlation Functionals.

Author information

1
School of Chemistry, University of Nottingham , University Park, Nottingham, NG7 2RD, United Kingdom.
2
Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo , P.O. Box 1033, Blindern, N-0315, Oslo, Norway.

Abstract

We present the self-consistent implementation of current-dependent (hybrid) meta-generalized gradient approximation (mGGA) density functionals using London atomic orbitals. A previously proposed generalized kinetic energy density is utilized to implement mGGAs in the framework of Kohn-Sham current density functional theory (KS-CDFT). A unique feature of the nonperturbative implementation of these functionals is the ability to seamlessly explore a wide range of magnetic fields up to 1 au (∼235 kT) in strength. CDFT functionals based on the TPSS and B98 forms are investigated, and their performance is assessed by comparison with accurate coupled-cluster singles, doubles, and perturbative triples (CCSD(T)) data. In the weak field regime, magnetic properties such as magnetizabilities and nuclear magnetic resonance shielding constants show modest but systematic improvements over generalized gradient approximations (GGA). However, in the strong field regime, the mGGA-based forms lead to a significantly improved description of the recently proposed perpendicular paramagnetic bonding mechanism, comparing well with CCSD(T) data. In contrast to functionals based on the vorticity, these forms are found to be numerically stable, and their accuracy at high field suggests that the extension of mGGAs to CDFT via the generalized kinetic energy density should provide a useful starting point for further development of CDFT approximations.

PMID:
26575912
DOI:
10.1021/acs.jctc.5b00535

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