Bond-breaking excitations with diverging coupling matrix of response density functional theory from highest-level functionals

Robert van Meer and Oleg V. Gritsenko ()
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Robert van Meer: Computational Molecular Science Research Team, RIKEN Advanced Institute for Computational Science
Oleg V. Gritsenko: Section Theoretical Chemistry, VU University

The European Physical Journal B: Condensed Matter and Complex Systems, 2018, vol. 91, issue 6, 1-6

Abstract: Abstract Bond-breaking excitations ω α are the problematic case of adiabatic time-dependent density functional theory (TDDFT). The calculated ω α erroneously vanishes with the bond elongation, since the Hartree-exchange-correlation kernel and the corresponding response coupling matrix K of standard approximations lack the characteristic divergence in the dissociation limit. In this paper an approximation for K is proposed constructed from the highest-level functionals, in which both occupied and virtual Kohn-Sham orbitals participate with the weights w p . The latter provide the correct divergence of K in the limit of dissociating two-electron bond. The present K brings a decisive contribution to the energy of the 1Σ u + in the prototype H2 molecule calculated for various H-H separations. At shorter separations it improves ω α compared to the zero-order TDDFT estimate, while at the largest separation it reproduces near-saturation of the reference excitation energy.

Date: 2018
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DOI: 10.1140/epjb/e2018-90088-6

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