Jump to main content
Jump to site search


Performance of TDDFT with and without spin-flip in trajectory surface hopping dynamics: cistrans azobenzene photoisomerization

Author affiliations

Abstract

Time-dependent density functional theory (TDDFT) with and without a spin-flip scheme is extensively compared in on-the-fly trajectory surface hopping molecular dynamics with a global switching (GS) algorithm. The simulation is performed for cistrans azobenzene photoisomerization following the excitation to the S1(nπ*) state that is involved in a conical intersection (CI) between ground and first excited states. This CI is found correctly to be a single-cone (artificial double-cone) structure computed by the TDDFT method with (and without) spin-flip. Nevertheless, simulated quantum yields and lifetimes are in very good agreement; 0.43 and 63 fs (0.34 and 62 fs) for cis-to-trans isomerization, and 0.11 and 2200 fs (0.13 and 1040 fs) for trans-to-cis isomerization, by TDDFT with (and without) a spin-flip scheme. Distributions of excited-state decay, hopping spots and products, as well as typical trajectories have similar patterns and behaviors with and without spin-flip. The global switching trajectory surface hopping method is demonstrated to be well suited to TDDFT on-the-fly dynamic simulation with and without spin-flip. For comparison, previous simulations with the CASSCF method and Tully's fewest-switches trajectory surface hopping method are also addressed.

Graphical abstract: Performance of TDDFT with and without spin-flip in trajectory surface hopping dynamics: cis–trans azobenzene photoisomerization

Back to tab navigation

Supplementary files

Publication details

The article was received on 18 Jun 2018, accepted on 28 Aug 2018 and first published on 29 Aug 2018


Article type: Paper
DOI: 10.1039/C8CP03851A
Citation: Phys. Chem. Chem. Phys., 2018, Advance Article
  •   Request permissions

    Performance of TDDFT with and without spin-flip in trajectory surface hopping dynamics: cistrans azobenzene photoisomerization

    L. Yue, Y. Liu and C. Zhu, Phys. Chem. Chem. Phys., 2018, Advance Article , DOI: 10.1039/C8CP03851A

Search articles by author

Spotlight

Advertisements