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Photodynamic control using field optimized initial state: A mechanistic investigation of selective control with application to IBr and HI photodissociation

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Title Photodynamic control using field optimized initial state: A mechanistic investigation of selective control with application to IBr and HI photodissociation
 
Creator VANDANA, K
MISHRA, MK
 
Subject femtosecond laser-pulses
curve-crossing reactions
grid hamiltonian method
unimolecular reactions
chemical-reaction
excitation
multiphoton
dynamics
photofragmentation
molecules
 
Description The probability density profiles from the optimal superpositions of the field free vibrational eigenstates which maximize flux out of the desired photodissociation channels are examined for IBr and HI molecules. Analysis of the structure in these optimal superposition states obtained by applying the Rayleigh-Ritz variational procedure to the time integrated flux operator shows that the transfer of probability density to appropriate areas of the Franck-Condon region on the excited surfaces is responsible for selective flux maximization out of different channels. Localizing the wave packet on the more repulsive part of the higher curve facilitates fast diabatic exit out of the upper channel and transition to the less repulsive part promotes slow adiabatic exit out of the lower channel. This mechanism is further probed by utilizing time dependent wave packet dynamics to obtain absorption spectra and branching ratios using full Fourier transform of the autocorrelation functions for these field optimized initial states. The results corroborate the central role of altered spatial profile of the initial state in selective control of photodissociation. (C) 1999 [S0021-9606(99)00610-8].
 
Publisher AMER INST PHYSICS
 
Date 2011-07-16T11:44:39Z
2011-12-26T12:49:45Z
2011-12-27T05:35:25Z
2011-07-16T11:44:39Z
2011-12-26T12:49:45Z
2011-12-27T05:35:25Z
1999
 
Type Article
 
Identifier JOURNAL OF CHEMICAL PHYSICS, 110(11), 5140-5148
0021-9606
http://dx.doi.org/10.1063/1.478409
http://dspace.library.iitb.ac.in/xmlui/handle/10054/4419
http://hdl.handle.net/10054/4419
 
Language en