TY - JOUR

T1 - Dual-Functional Tamm-Dancoff Approximation with Self-Interaction-Free Orbitals

T2 - Vertical Excitation Energies and Potential Energy Surfaces near an Intersection Seam

AU - Shu, Yinan

AU - Parker, Kelsey A.

AU - Truhlar, Donald G.

PY - 2017/12/28

Y1 - 2017/12/28

N2 - 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.

AB - 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.

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U2 - 10.1021/acs.jpca.7b11400

DO - 10.1021/acs.jpca.7b11400

M3 - Article

C2 - 29200293

AN - SCOPUS:85040109280

VL - 121

SP - 9728

EP - 9735

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 51

ER -