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Title: Substituent effects on dynamics at conical intersections: Allene and methyl allenes

We report a joint experimental and theoretical study on the ultrafast excited state dynamics of allene and a series of its methylated analogues (1,2-butadiene, 1,1-dimethylallene, and tetramethylallene) in order to elucidate the conical intersection mediated dynamics that give rise to ultrafast relaxation to the ground electronic state. We use femtosecond time-resolved photoelectron spectroscopy (TRPES) to probe the coupled electronic-vibrational dynamics following UV excitation at 200 nm (6.2 eV). Ab initio multiple spawning (AIMS) simulations are employed to determine the mechanistic details of two competing dynamical pathways to the ground electronic state. In all molecules, these pathways are found to involve as follows: (i) twisting about the central allenic C–C–C axis followed by pyramidalization at one of the terminal carbon atoms and (ii) bending of allene moiety. Importantly, the AIMS trajectory data were used for ab initio simulations of the TRPES, permitting direct comparison with experiment. For each molecule, the decay of the TRPES signal is characterized by short (30 fs, 52 fs, 23 fs) and long (1.8 ps, 3.5 ps, [306 fs, 18 ps]) time constants for 1,2-butadiene, 1,1-dimethylallene, and tetramethylallene, respectively. However, AIMS simulations show that these time constants are only loosely related to the evolution of electronic charactermore » and actually more closely correlate to large amplitude motions on the electronic excited state, modulating the instantaneous vertical ionization potentials. Furthermore, the fully substituted tetramethylallene is observed to undergo qualitatively different dynamics, as displacements involving the relatively massive methyl groups impede direct access to the conical intersections which give rise to the ultrafast relaxation dynamics observed in the other species. These results show that the branching between the “twisting” and “bending” pathways can be modified via the selective methylation of the terminal carbon atoms of allene. The interplay between inertial and potential effects is a key to understanding these dynamical branching pathways. The good agreement between the simulated and measured TRPES confers additional confidence to the dynamical picture presented here.« less
Authors:
 [1] ;  [2] ; ;  [1] ;  [3] ;  [3] ;  [1] ;  [3]
  1. Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5 (Canada)
  2. State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071 (China)
  3. (Canada)
Publication Date:
OSTI Identifier:
22493616
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 144; Journal Issue: 1; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALLENE; ATOMS; BRANCHING RATIO; BUTADIENE; CARBON; COMPARATIVE EVALUATIONS; EV RANGE; EXCITATION; EXCITED STATES; METHYLATION; MOLECULES; PHOTOELECTRON SPECTROSCOPY; POTENTIALS; PROBES; RELAXATION; TIME RESOLUTION