Fast Nonadiabatic Molecular Dynamics via Spin-Flip Time-Dependent Density-Functional Tight-Binding Approach: Application to Nonradiative Relaxation of Tetraphenylethylene with Locked Aromatic Rings

Hiroki Uratani, Toshiki Morioka, Takeshi Yoshikawa, Hiromi Nakai

Research output: Contribution to journalArticlepeer-review

1 Citation (Scopus)

Abstract

Nonadiabatic dynamics around conical intersections between ground and excited states are crucial to understand excited-state phenomena in complex chemical systems. With this background in mind, we present an approach combining fewest-switches trajectory surface hopping and spin-flip (SF) time-dependent (TD) density-functional tight binding (DFTB), which is a simplified version of SF-TD density functional theory (DFT) with semiempirical parametrizations, for computationally efficient nonadiabatic molecular dynamics simulations. The estimated computational time of the SF-TD-DFTB approach is several orders of magnitude lower than that of SF-TD-DFT. In addition, the proposed method reproduces the time scales and quantum yields in photoisomerization reactions of azobenzene at a level comparable with conventional ab initio approaches, demonstrating reasonable accuracy. Finally, we report a practical application of the developed technique to explore the nonradiative relaxation processes of tetraphenylethylene and its derivative with torsionally locked aromatic rings and discuss the effect of locking the rings on the excited-state lifetime.

Original languageEnglish
Pages (from-to)7299-7313
Number of pages15
JournalJournal of chemical theory and computation
Volume16
Issue number12
DOIs
Publication statusPublished - 2020 Dec 8

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

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