Two-color two-photon excited fluorescence of indole: determination of wavelength-dependent molecular parameters.

We present a detailed study of two-color two-photon excited fluorescence in indole dissolved in propylene glycol. Femtosecond excitation pulses at effective wavelengths from 268 to 293.33 nm were used to populate the two lowest indole excited states (1)La and (1)Lb and polarized fluorescence was then detected. All seven molecular parameters and the two-photon polarization ratio Ω containing information on two-photon absorption dynamics, molecular lifetime τf, and rotation correlation time τrot have been determined from experiment and analyzed as a function of the excitation wavelength. The analysis of the experimental data has shown that (1)Lb-(1)La inversion occurred under the conditions of our experiment. The two-photon absorption predominantly populated the (1)La state at all excitation wavelengths but in the 287-289 nm area which contained an absorption hump of the (1)Lb state 0-0 origin. The components of the two-photon excitation tensor S were analyzed giving important information on the principal tensor axes and absorption symmetry. The results obtained are in a good agreement with the results reported by other groups. The lifetime τf and the rotation correlation time τrot showed no explicit dependence on the effective excitation wavelength. Their calculated weighted average values were found to be τf = 3.83 ± 0.14 ns and τrot = 0.74 ± 0.06 ns.

The role of the Coriolis interaction on vector correlations in molecular predissociation: excitation of isolated rotational lines.

We present the full quantum mechanical expressions for the polarization differential cross sections of the photofragments produced in slow predissociation of a parent molecule via isolated rotational branches. Both radial and Coriolis nonadiabatic interactions between the molecular potential energy surfaces have been taken into account. The expressions describe the recoil angle distribution of the photofragments and the distributions of the photofragment angular momentum polarization (orientation and alignment) in terms of the anisotropy parameters of the ranks K=0,1,2. The explicit expressions for the anisotropy parameters are presented and analyzed which contain contributions from different possible photolysis mechanisms including incoherent, or coherent optical excitation of the parent molecule followed by the radial, or Coriolis nonadiabatic transitions to the dissociative states. The obtained expression for the zeroth-rank anisotropy parameter beta is valid for any molecule and for an arbitrary value of the molecular total angular momentum J. The expressions for the orientation (K=1) and alignment (K=2) anisotropy parameters are given in the high-J limit in terms of the generalized dynamical functions which were analyzed for the case of photolysis of linear/diatomic molecules. As shown, the Coriolis nonadiabatic interaction results in several new photolysis mechanisms which can play an important role in the predissociation dynamics.

The parity-adapted basis set in the formulation of the photofragment angular momentum polarization problem: the role of the Coriolis interaction.

We present a theoretical framework for calculating the recoil-angle dependence of the photofragment angular momentum polarization taking into account both radial and Coriolis nonadiabatic interactions in the diatomic/linear photodissociating molecules. The parity-adapted representation of the total molecular wave function has been used throughout the paper. The obtained full quantum-mechanical expressions for the photofragment state multipoles have been simplified by using the semiclassical approximation in the high-J limit and then analyzed for the cases of direct photodissociation and slow predissociation in terms of the anisotropy parameters. In both cases, each anisotropy parameter can be presented as a linear combination of the generalized dynamical functions fK(q,q',q,q') of the rank K representing contribution from different dissociation mechanisms including possible radial and Coriolis nonadiabatic transitions, coherent effects, and the rotation of the recoil axis. In the absence of the Coriolis interactions, the obtained results are equivalent to the earlier published ones. The angle-recoil dependence of the photofragment state multipoles for an arbitrary photolysis reaction is derived. As shown, the polarization of the photofragments in the photolysis of a diatomic or a polyatomic molecule can be described in terms of the anisotropy parameters irrespective of the photodissociation mechanism.

Multiphoton processes of CO at 230 nm.

High resolution kinetic energy release spectra were obtained for C(+) and O(+) from CO multiphoton ionization followed by dissociation of CO(+). The excitation was through the CO (B (1)Sigma(+)) state via resonant two-photon excitation around 230 nm. A total of 5 and 6 photons are found to contribute to the production of carbon and oxygen cations. DC slice and Megapixel ion imaging techniques were used to acquire high quality images. Major features in both O(+) and C(+) spectra are assigned to the dissociation of some specific vibrational levels of CO(+)(X (2)Sigma(+)). The angular distributions of C(+) and O(+) are very distinct and those of various features of C(+) are also different. A dramatic change of the angular distribution of C(+) from dissociation of CO(+)(X (2)Sigma(+), nu(+) = 1) is attributed to an accidental one-photon resonance between CO(+)(X (2)Sigma(+), nu(+) = 1) and CO(+)(B (2)Sigma(+), nu(+) = 0) and explained well by a theoretical model. Both kinetic energy release and angular distributions were used to reveal the underlying dynamics.