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

5 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

Bibliographical note

Funding Information:
K.P. acknowledges a 2016−2017 Excellence Fellowship in Chemistry at the University of Minnesota. This work was supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award DESC0015997.

Publisher Copyright:
© 2017 American Chemical Society.

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