Intramolecular dynamics by photoelectron spectroscopy. I. Application to N+2, HBr+, and HCN+

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Abstract
The Fourier transform of an optical electronic spectrum leads to an autocorrelation function C(t) which describes the evolution in time of the wave packet created by the Franck–Condon transition, as it propagates on the potential energy surface of the electronic upper state. This correlation function is equal to the modulus of the overlap integral between the initial position of the wave packet and its instantaneous position at time. The original data resulting from an experimentally determined spectral profile must be corrected for finite energy resolution, rotational, and spin‐orbit effects. The behavior of the system can then be followed up to a time of the order of 10−13 s, i.e., during the first few vibrations which follow immediately the electronic transition. The method is applied to photoelectron spectra and the results are compared to the available information on potential energy surfaces of ionized molecules, in order to study their unimolecular dissociation dynamics. In the case of the X 2Σ+g, A 2Πu, and B 2Σ+u states of N+2, an oscillatory pattern is obtained for the correlation function. This indicates that the nuclear motion is taking place in a bound potential. Effects due to anharmonicity are visible in the case of the A 2Πu state. The study of the X 2Π state of HBr+ demonstrates the overwhelming importance of spin‐orbit coupling when heavy atoms are present in the molecule. Finally, the method is applied to a polyatomic molecule. The potential energy surface of the ? 2Σ+ state of HCN+ is characterized by two energy minima separated by a saddle point. The corresponding band in the photoelectron spectrum is characterized by an irregular vibrational structure superimposed upon a broad continuum. A study of the correlation function shows that the wave packet undergoes a complicated, two‐component motion: while oscillating across the saddle point, it spreads away at the same time along the dissociative degree of freedom. This gives information on the rate of energy redistribution within the molecule.