No Access Submitted: 25 March 1991 Accepted: 21 June 1991 Published Online: 31 August 1998
J. Chem. Phys. 95, 4809 (1991); https://doi.org/10.1063/1.461699
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  • Institut für Physikalische und Theoretische Chemie, Technische Universität München, Lichtenbergstrasse 4, W‐8046 Garching, Germany
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  • Wieland Habenicht
  • Georg Reiser
  • Klaus Müller‐Dethlefs
Rotationally resolved ‘‘zero kinetic energy (ZEKE)’’ electron spectra of ammonia obtained in a 2+1 photon two‐color pump–probe experiment are reported. The rovibronic states with J=3, K=1 (ortho‐NH3) and J=3, K=2 (para‐NH3) in the B̃ (1E) v2=2 state are used as intermediate resonances. Rotational energy levels of the NH+3 ion in two vibrational states of the X̃+ (2A2) electronic ground state, v+2 =1 and 2, are observed in the ZEKE spectra. The rotational constants are: B+=10.19±0.03 cm−1 and C+=5.30±0.04 cm−1 for v+2 =1, and B+ =9.77±0.04 cm−1 and C+ =5.39±0.05 cm−1 for v+2 =2. The adiabatic ionization energies are determined as 83 062.5±1 cm−1 for X̃+ v2=1 and 84 002.9±1 cm−1 for X̃+ v2=2, with respect to the lowest (unoccupied) v2=0+, J=0, K=0, Γevr=A1 rotational state of the X̃ (1A1) electronic ground state of NH3. The observed propensity rules for the change in K quantum number ion←neutral in the rotational ZEKE transitions are explained from ‘‘near symmetry’’conservation rules in electronically allowed transitions.
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