Varella, Márcio T. do N. and Arasaki, Yasuki and Ushiyama, Hiroshi and McKoy, Vincent and Takatsuka, Kazuo (2006) Time-resolved photoelectron spectroscopy of proton transfer in the ground state of chloromalonaldehyde: Wave-packet dynamics on effective potential surfaces of reduced dimensionality. Journal of Chemical Physics, 124 (15). Art. No. 154302. ISSN 0021-9606 http://resolver.caltech.edu/CaltechAUTHORS:VARjcp06
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We report on a simple but widely useful method for obtaining time-independent potential surfaces of reduced dimensionality wherein the coupling between reaction and substrate modes is embedded by averaging over an ensemble of classical trajectories. While these classically averaged potentials with their reduced dimensionality should be useful whenever a separation between reaction and substrate modes is meaningful, their use brings about significant simplification in studies of time-resolved photoelectron spectra in polyatomic systems where full-dimensional studies of skeletal and photoelectron dynamics can be prohibitive. Here we report on the use of these effective potentials in the studies of dump-probe photoelectron spectra of intramolecular proton transfer in chloromalonaldehyde. In these applications the effective potentials should provide a more realistic description of proton-substrate couplings than the sudden or adiabatic approximations commonly employed in studies of proton transfer. The resulting time-dependent photoelectron signals, obtained here assuming a constant value of the photoelectron matrix element for ionization of the wave packet, are seen to track the proton transfer.
|Additional Information:||©2006 American Institute of Physics (Received 14 July 2005; accepted 8 March 2006; published online 17 April 2006) This work has been supported by Fundação de Amparo à Pesquisa do Estado de São Paulo–FAPESP (Brazil), by the National Science Foundation (U.S.), and by a Grant-in-Aid for Basic Science and the 21st Century COE Program for Frontier in Fundamental Chemistry from the Ministry of Education Science Sports and Culture of Japan.|
|Subject Keywords:||organic compounds; chemical exchanges; potential energy surfaces; reaction kinetics theory; time resolved spectra; photoelectron spectra; spectrochemical analysis; ground states|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Archive Administrator|
|Deposited On:||27 Jul 2006|
|Last Modified:||26 Dec 2012 08:57|
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