Photophysics of fulvene under the non-resonant stark effect. Shaping the conical intersection seam.

摘要: We introduce a mechanistic strategy to control the excited state lifetime of fulvene based on shaping topography an extended seam intersection with non-resonant dynamic Stark effect. Fulvene has very short due energetically accessible which lies along methylene torsion coordinate, and initial decay occurs at segment around planar conical structure. have followed three-step approach simulate control. First, we calculated effect electric field potential energy surface ab initio level, including in self-consistent way. The relative is increased by field. In second step carrying out MCTDH quantum dynamics propagations under static derive main mechanisms. At moderately intense fields (e ≤ 0.03 a.u.) faster as compared free case because vibrational overlap between ground functions increased. However, more = 0.04 inaccessible slower time scale, twisted geometries. third step, over exerted acceleration improved does not occur, but can be made 0.08 a.u. results show viability our photophysics topology seam, they prove that nature crucial for simulating understanding