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Time-resolved velocity map ion imaging study of NH3 photodissociation

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Wells, Kym L., Perriam, Gareth and Stavros, Vasilios G. (2009) Time-resolved velocity map ion imaging study of NH3 photodissociation. Journal of Chemical Physics, Vol.130 (No.7). article no.074308. doi:10.1063/1.3072763

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Official URL: http://dx.doi.org/10.1063/1.3072763

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Abstract

Following excitation of the A state nu(')(2)=4 mode in ammonia, we show how the time scale to dissociation of the N-H bond depends on the internal energy imparted to the NH2 photofragment. Using a combination of femtosecond pump/probe spectroscopy and velocity map ion imaging techniques, the time and energy resolved H-atom elimination can be directly related to the nonadiabatic nature of the photodissociation for high kinetic energy H atoms with evidence for adiabatic dynamics to dissociation giving the lowest energy H atoms. Extrapolation of the time scales for dissociation versus internal energy of the NH2 photofragment implies that dissociation to the vibrationless ground state of NH2 occurs in < 50 fs, in very good agreement with frequency resolved measurements. The anisotropy of the H fragments with the highest kinetic energies seems to also suggest that the NH2 partner fragment comes off with very low rotational excitation.

Item Type: Journal Article
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Science, Engineering and Medicine > Science > Chemistry
Library of Congress Subject Headings (LCSH): Photodissociation, Chemical kinetics, Imaging systems in chemistry
Journal or Publication Title: Journal of Chemical Physics
Publisher: American Institute of Physics
ISSN: 0021-9606
Official Date: 21 February 2009
Dates:
DateEvent
21 February 2009Published
Volume: Vol.130
Number: No.7
Number of Pages: 5
Page Range: article no.074308
DOI: 10.1063/1.3072763
Status: Peer Reviewed
Publication Status: Published
Access rights to Published version: Restricted or Subscription Access
Funder: Royal Society (Great Britain), Engineering and Physical Sciences Research Council (EPSRC), University of Warwick
Grant number: EP/E011187 (EPSRC)

Data sourced from Thomson Reuters' Web of Knowledge

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