Ab initio based surface-hopping dynamics study on ultrafast internal conversion in cyclopropanone

  • Cui G
  • Fang W
  • 9


    Mendeley users who have this article in their library.
  • 12


    Citations of this article.


Cyclopropanone exhibits an intriguing phenomenon that the fluorescence from the S(1) state disappears below 365 nm. This is ascribed to the ultrafast S(1) → S(0) internal conversion process via conical intersection, which deprives opportunity of the fluorescence emission. In this work, we have used ab initio based surface hopping dynamics method to study vibrational-mode-dependent S(1) → S(0) internal conversion of cyclopropanone. A new conical intersection between the S(1) and S(0) states is determined by the state-averaged CASSCF/cc-pVDZ calculations, which is confirmed to play a critical role in the ultrafast S(1) → S(0) internal conversion by the nonadiabatic dynamics simulations. It is found that the internal conversion occurs more efficiently when the initial kinetic energies are distributed in the four vibrational modes related to the C═O group, especially in the C-O stretching and the O-C-C-C out-of-plane torsional modes. Meanwhile, the S(1) lifetime and the time scale of the S(1) → S(0) internal conversion are estimated by the ab initio based dynamics simulations, which is consistent with the ultrafast S(1) → S(0) internal conversion and provides further evidence that the ultrafast internal conversion is responsible for the fluorescence disappearance of cyclopropanone.

Get free article suggestions today

Mendeley saves you time finding and organizing research

Sign up here
Already have an account ?Sign in

Find this document


  • Ganglong Cui

  • Weihai Fang

Cite this document

Choose a citation style from the tabs below

Save time finding and organizing research with Mendeley

Sign up for free