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Laser assisted control of selective bond dissociation in HOD - some mechanistic insights

DSpace at IIT Bombay

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Title Laser assisted control of selective bond dissociation in HOD - some mechanistic insights
 
Creator SARMA, M
ADHIKARI, S
MISHRA, MK
 
Subject optimized initial-state
1st absorption-band
dependent schrodinger-equation
dna-strand breaks
photodissociation dynamics
ev electrons
photodynamic control
molecular-dynamics
chemical-reactions
model simulations
selective control
hod photodissociation
flux maximisation
trans-modal flow
expectation value
downhill motion
 
Description Quantum dynamical calculations on HOD subjected to different combinations of IR and UV pulses have been made to isolate field attributes which maximise selectivity and yield in the photodissociation of the desired O-H/O-D bond. Results from IR+UV pulse combinations which provide very high selectivity and/or yield are analysed in detail using population transfer, probability density flow, and flux variations to obtain microdynamic details favouring selectivity and yield. The expectation values for stretch and momentum in O-H and O-D bonds of the H-O-D molecule subjected to UV pulses effecting selective cleavage of these bonds have been analysed to decipher the mechanistic basis of selective dissociation. Fully quantum dynamical calculations using both the ground and excited potential energy surfaces with different initial states and UV pulses reveal that prior stretch in a bond before transferring it to the repulsive first excited state ensures preferential dissociation of this bond. The sampling of large stretch values and a quick downhill motion in the channel corresponding to dissociation of the prestretched bond on the upper surface are seen to underlie this preferential dissociation.
 
Publisher TAYLOR & FRANCIS LTD
 
Date 2011-08-31T01:22:18Z
2011-12-26T12:59:16Z
2011-12-27T05:50:24Z
2011-08-31T01:22:18Z
2011-12-26T12:59:16Z
2011-12-27T05:50:24Z
2009
 
Type Article
 
Identifier MOLECULAR PHYSICS, 107(8-12), 939-961
0026-8976
http://dx.doi.org/10.1080/00268970802708934
http://dspace.library.iitb.ac.in/xmlui/handle/10054/12531
http://hdl.handle.net/10054/12531
 
Language en