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

Sarma, Manabendra ; Adhikari, S. ; Mishra, M. K. (2009) Laser assisted control of selective bond dissociation in HOD-some mechanistic insights Molecular Physics, 107 (8-12). pp. 939-961. ISSN 0026-8976

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Official URL: http://www.informaworld.com/smpp/content~db=all~co...

Related URL: http://dx.doi.org/10.1080/00268970802708934

Abstract

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.

Item Type:Article
Source:Copyright of this article belongs to Taylor and Francis Ltd.
Keywords:Selective Control; HOD Photodissociation; Flux Maximisation; Trans-modal Flow; Expectation Value; Downhill Motion
ID Code:20183
Deposited On:20 Nov 2010 14:53
Last Modified:08 Jun 2011 04:29

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