Dual-Functional Tamm-Dancoff Approximation with Self-Interaction-Free Orbitals: Vertical Excitation Energies and Potential Energy Surfaces near an Intersection Seam

Yinan Shu, Kelsey A. Parker, Donald G. Truhlar

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

Recently we have developed the dual-functional Tamm-Dancoff approximation (DF-TDA) method. DF-TDA is an alternative to linear-response time-dependent density functional theory (LR-TDDFT) with the advantage of providing a correct double-cone topology of S1/S0 conical intersections. In the DF-TDA method, we employ different functionals, which are denoted G and F, for orbital optimization and Hamiltonian construction. We use the notation DF-TDA/G:F. In the current work, we propose that G be the same as F except for having 100% Hartree-Fock exchange. We use the notation F100 to denote functional F with this modification. A motivation for this is that functionals with 100% Hartree-Fock exchange are one-electron self-interaction-free. Here we validate the use of F100/M06 to compute vertical excitation energies and the global potential energy surface of ammonia near a conical intersection to further validate the F100 method for photochemical problems.

Original languageEnglish (US)
Pages (from-to)9728-9735
Number of pages8
JournalJournal of Physical Chemistry A
Volume121
Issue number51
DOIs
StatePublished - Dec 28 2017

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