Photodissociation of ClNO in the 2 ¹A′ State: Computational and Experimental NO Product State Distributions

Abstract

Ultrafast photodissociation of the 2 1A′ 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 1A′ 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 1A′ 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.

NEXAFS and XPS studies of nitrosyl chloride

“…5 In more recent studies the photolysis reactions of ClNO have extensively been investigated both theoretically and experimentally in the UV-visible spectral range. [8][9][10][11][12][13][14] In particular, in the photon energy range of 4-7 eV such investigations revealed a strong broad absorption band consisting of three contributions, the most intense of which has a maximum at 6.3 eV and is associated with the formation of the 4 1 A 0 excited state. 8,9,11,13 4 1 A 0 was assigned to electron excitation from the HOMO to the lowest unoccupied MO + 1 (LUMO + 1) (14a 0 ).…”

Double Photoionization of Nitrosyl Chloride by Synchrotron Radiation in the 24–70 eV Photon Energy Range

“…Despite various studies already conducted concerning photo-induced processes on ClNO using photons in the ultraviolet (UV)-visible [ 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 ] and infrared [ 15 , 16 , 17 ] energy range, no data on its double photoionization by direct ejection of two valence electrons are available.…”