Dependence of NO rotational photoionization propensity rules on electron kinetic energy

In order to study the effect of photoelectron kinetic energy on rotational photoionization propensity rules, rotationally resolved laser photoelectron spectra were measured for excitation of specific rovibronic levels in the D 2Sigma+ (3psigma) Rydberg state of NO and their subsequent ionization by radiation at several wavelengths. The measured and calculated ion rotational branching ratios both show a significant dependence on photoelectron energy. Comparison between experimental data and theoretical calculations suggests that a strong DeltaN=0 peak in the spectra is caused by an interaction between particular vibronic levels of the A 2Sigma+ (v=4) and D 2Sigma+ (v=0) Rydberg states

TWO-COLOR PICOSECOND PHOTOELECTRON STUDY OF IVR IN ALKYLANILINE AND ALKYLBENZENE MOLECULES

Author Institution: Department of Chemistry, University of IndianaTime dependent intramolecular vibrational relaxation (IVR) in the $^{1}B_{2}$ excited electronic state of alkylaniline and alkylbenzene molecules was directly monitored by employing a two-photon ionization process. Photoelectrons were produced by two-color pump-probe ionization induced by picosecond laser pulses impinging on a jet-cooled molecular beam. Their kinetic energies of photoelectrons were measured by a time of flight method. With the picosecond pump laser tuned to different vibrational modes in the excited electronic state of these molecules and the probe laser adjusted to the different delay times, photoelectron spectra were recorded. The extended chain conformation (trans) and the coiled chain conformation (gauche) exhibit remarkably different IVR behavior. Comparison of the rates of IVR in these molecules will be made. The conformational dependence of the ionization potential in these molecules will also be discussed