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Photodissociation of ClNO in the 2 1 A′ State: Computational and Experimental NO Product State Distributions
Author(s) -
Jones Kiera M.,
Milkiewicz Jadwiga A.,
Whitaker Benjamin J.,
Sage Alan G.,
Worth Graham A.
Publication year - 2013
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201200999
Subject(s) - chemistry , excited state , photodissociation , atomic physics , multireference configuration interaction , excitation , potential energy surface , dipole , potential energy , wave packet , configuration interaction , physics , ab initio , quantum mechanics , photochemistry , organic chemistry
Ultrafast photodissociation of the 2 1 A′ state of ClNO, which has an absorption spectrum peaking at 335 nm, is studied by computational and experimental methods. New potential‐energy surfaces are calculated for the 1 and 2 1 A′ states at the multireference configuration interaction (MRCI) level. Wavepacket dynamics simulations performed both exactly and by using the multiconfiguration time‐dependent Hartree method yield essentially identical results. Transition dipole moments at a range of geometries are included in these calculations to correctly model the excitation. Vibrational and rotational state distributions of the NO product are obtained both computationally by analysing the quantum flux on the 2 1 A′ surface and experimentally by use of 3D resonant multiphoton ionisation (REMPI), a variant of the velocity map imaging technique. The nascent NO is found to be only marginally vibrationally excited, with 91 % formed in v =0. The calculated NO rotational distribution peaks in the j =45–55 region, which compares favourably to experiment.