Photodissociation of ND3 and ND2H at 193.3 nm: Symmetry dependence of the rotational distributions and vibrational excitation of the ND2 ((A)over-tilde(2)A(1)) fragment

G. Duxbury, Jonathan. P. Reid

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Abstract

A rotational and vibrational analysis has been made of the ND2 (A) over tilde 2A(1) - (X) over tilde B-2(1) emission spectrum produced from the ultraviolet laser induced dissociation of both jet cooled and room temperature deuterated ammonia, ND3, and di-deuterated ammonia, ND2H. The pattern of the strong features in the emission spectra is very different in the fragmentation of ND3 and ND2H, with a much wider range of angular momentum states being observed from the photolysis of the predissociative ((A) over tilde) state of unsymmetrical parent ND2H ((A) over tilde). The analysis is based upon the earlier studies of the electronic spectrum of ND2, and model calculation based upon the stretch-bender Renner-Teller Hamiltonian. The spectra consist of two types, transitions from a narrow distribution of high angular momentum states in the photolysis of ND3 and ND2H, and in the photolysis of ND2H strong emission from threshold states in three high energy regions. The threshold states are in the third bending level, upsilon'(2) = 3 of the ND2 ((A) over tilde) state, and have no angular momentum about the axis of least moment of inertia, K'(a) = 0.
Original languageEnglish
Pages (from-to)123-135
Number of pages13
JournalJournal of Molecular Spectroscopy
Volume267
Issue number1-2 special issue
Early online date11 Mar 2011
DOIs
Publication statusPublished - May 2011

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Keywords

  • rovibronic energies
  • photodissociation
  • stretch-bender calculations
  • electronic ground-state
  • high angular-momentum
  • rotational distributions
  • electronic spectra
  • absortio
  • vibronic coupling
  • fermi resonance
  • state ammonia molecules
  • renner-teller effect
  • nd3
  • nd2h
  • symmetry dependence
  • vibrational excitation
  • nd2
  • fragment

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