Volume 157, 2012

Between ethylene and polyenes - the non-adiabatic dynamics of cis-dienes

Abstract

Using Ab Initio Multiple Spawning (AIMS) with a Multi-State Multi-Reference Perturbation theory (MS-MR-CASPT2) treatment of the electronic structure, we have simulated the non-adiabatic excited state dynamics of cyclopentadiene (CPD) and 1,2,3,4-tetramethyl-cyclopentadiene (Me4-CPD) following excitation to S1. It is observed that torsion around the carbon–carbon double bonds is essential in reaching a conical intersection seam connecting S1 and S0. We identify two timescales; the induction time from excitation to the onset of population transfer back to S0 (CPD: ∼25 fs, Me4-CPD: ∼71 fs) and the half-life of the subsequent population transfer (CPD: ∼28 fs, Me4-CPD: ∼48 fs). The longer timescales for Me4-CPD are a kinematic consequence of the inertia of the substituents impeding the essential out-of-plane motion that leads to the conical intersection seam. A bifurcation is observed on S1 leading to population transfer being attributable, in a 5 : 2 ratio for CPD and 7 : 2 ratio for Me4-CPD, to two closely related conical intersections. Calculated time-resolved photoelectron spectra are in excellent agreement with experimental spectra validating the simulation results.

Supplementary files

Article information

Article type
Paper
Submitted
23 Mar 2012
Accepted
30 Apr 2012
First published
02 May 2012

Faraday Discuss., 2012,157, 193-212

Between ethylene and polyenes - the non-adiabatic dynamics of cis-dienes

T. S. Kuhlman, W. J. Glover, T. Mori, K. B. Møller and T. J. Martínez, Faraday Discuss., 2012, 157, 193 DOI: 10.1039/C2FD20055D

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