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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.
†Dedicated to Professor H.F. Schaefer III on his 65th birthday.
Acknowledgements
This research has been supported by grants from the Board of Research in Nuclear Sciences (Grant No. 2007/37/41-BRNS/2103) and Department of Science and Technology (DST) (Grant No. SR/S1/PC-30/2006), India to MKM. M.S. acknowledges support from CSIR, India (SRF, F. NO. 9/87(336)/2003-EMR-I) and IIT Guwahati (Grant No. SG/CHM/P/MS/1). SA is pleased to acknowledge Department of Science and Technology (DST), India for partial financial support through the project No. SR/S1/PC-13/2008.
Notes
†Dedicated to Professor H.F. Schaefer III on his 65th birthday.