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Femtosecond resonance-enhanced multiphoton-ionization photoelectron spectrum of ammonia

Journal Article · · Physical Review. A
 [1]; ; ; ; ;  [2]
  1. State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071 (China)
  2. State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China)

We have studied the multiphoton dissociation dynamics of the E-tilde{sup '} {sup 1}A{sub 1}{sup '} Rydberg state of ammonia (NH{sub 3}) on a homebuilt femtosecond pump-probe system by resonance-enhanced multiphoton ionization photoelectron (REMPI-PE) spectroscopy. The highly excited Rydberg state, E-tilde{sup '1} A{sub 1}{sup '}, of ammonia was accessed by two 267 nm pump photons and then ionized by a 401 nm probe pulse delayed in time. The variation of the REMPI-PE spectra of ammonia with pump-probe delay time provides valuable information on the dynamics of the excited intermediate accessed by the pump pulse. We find that the Frank-Condon preferred transition during ionization does not occur for {delta}{upsilon}{sub 1}=0 but for {delta}{upsilon}{sub 1}=1, which implies that the intermediate has a different geometry from the ionic ground state. Different dynamical behavior has been observed for each of the transitions {delta}{upsilon}{sub 1}=0,1,2,3, giving a full temporal description of the excited intermediate state by projection onto the eigenspace of the ionic ground state.

OSTI ID:
20974771
Journal Information:
Physical Review. A, Journal Name: Physical Review. A Journal Issue: 5 Vol. 74; ISSN 1050-2947; ISSN PLRAAN
Country of Publication:
United States
Language:
English