loading page

The Role of the Transition Density in the S0 → S1 and S0 → S2 Transitions of Fulvene with Next Generation QTAIM
  • +4
  • LiLing Wang,
  • Alireza Azizi,
  • Tianlv Xu,
  • Michael Filatov,
  • Steven Kirk,
  • Martin Paterson,
  • Samantha Jenkins
LiLing Wang
Hunan Normal University

Corresponding Author:[email protected]

Author Profile
Alireza Azizi
Hunan Normal University
Author Profile
Tianlv Xu
Hunan Normal University
Author Profile
Michael Filatov
Universität Bonn
Author Profile
Steven Kirk
Hunan Normal University
Author Profile
Martin Paterson
Heriot Watt University
Author Profile
Samantha Jenkins
Hunan Normal University
Author Profile

Abstract

We present, for the first time the S0 → S1 (S01) and S0 → S2 (S02) transition densities for fulvene, using the 3-D next generation QTAIM constructed using the preferred direction of electronic charge density accumulation. There is a symmetrization of the position of the bond critical point (BCP) of the torsional C2-C6 BCP along the bond-path associated with the presence of a conical intersection (CI) between the ground and first excited state (S1). The corresponding transition density S0 → S1 (S01) displays hindered BCP motion that is associated with a large rearrangement of the total electronic charge density, made apparent by the form of a 3-D bond-path. The reaction pathway for the second excited state does not have an associated CI to an adjacent state along this path, or symmetrization of the BCP position for the S0 → S2 (S02) transition density, or hindered motion, or a large deviation in the 3-D bond-path. We hypothesize that the symmetrization of the position of the torsional C2-C6 BCP along a bond-path for an excited state pathway is associated with a CI, where the transition density BCP is hindered and as a consequence the electron density undergoes a large rearrangement, made apparent by the form of the 3-D bond-path.