Nonadiabatic Molecular Dynamics Study of the Relaxation Pathways of Photoexcited Cyclooctatetraene

Huajing Song, Yeonsig Nam, Daniel Keefer, Marco Garavelli, Shaul Mukamel, Sergei Tretiak

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)


In the current study, we present nonadiabatic (NAMD) and adiabatic molecular dynamics simulations of the transition-state dynamics of photoexcited cyclooctatetraene (COT). The equilibrium-state structure and absorption spectra are analyzed using the semiempirical Austin Model 1 potential. The NAMD simulations are obtained by a surface-hopping algorithm. We analyzed in detail an active excited to ground state relaxation pathway accompanied by an S2/S3(D2d) → S1(D8h) → S0(D4h) → S0(D2d) double-bond shifting mechanism. The simulated excitation lifetime is in good agreement with experiment. The first excited singlet state S1 plays a crucial role in the photochemistry. The obtained critical molecular conformations, energy barrier, and transition-state lifetime results will provide a basis for further investigations of the bond-order inversion and photoswitching process of COT.

Original languageEnglish
Pages (from-to)5716-5722
Number of pages7
JournalThe journal of physical chemistry letters
Issue number24
Publication statusPublished - 24 Jun 2021
Externally publishedYes


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