High-resolution zero kinetic energy electron spectroscopy of ammonia

Habenicht, Wieland; Reiser, Georg; Müller-Dethlefs, Klaus
October 1991
Journal of Chemical Physics;10/1/1991, Vol. 95 Issue 7, p4809
Academic Journal
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 B (1E‘) v2=2 state are used as intermediate resonances. Rotational energy levels of the NH+3 ion in two vibrational states of the X+ (2A‘2) 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 X+ v2=1 and 84 002.9±1 cm-1 for X+ v2=2, with respect to the lowest (unoccupied) v2=0+, J‘=0, K‘=0, Γevr=A1 rotational state of the X (1A’1) 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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