Semiclassical methods to simulate both steady and time-resolved photoelectron spectra are presented. These approaches provide spectra with absolute band shapes and vibrational broadening beyond the Condon approximation, using an ensemble of nuclear configurations built either via distribution samplings or nonadiabatic dynamics simulations. Two models to account for the electron kinetic energy modulation due to vibrational overlaps between initial and final states are discussed. As illustrative examples, the steady photoelectron spectra of imidazole and adenine and the time- and kinetic-energy-resolved photoelectron spectrum of imidazole were simulated within the frame of time-dependent density functional theory. While for steady spectra only electrons ejected with maximum allowed kinetic energy need to be considered, it is shown that to properly describe time-resolved spectra, electrons ejected with low kinetic energies must be considered in the simulations as well. The results also show that simulations based either on full computation of photoelectron cross section or on simple Dyson orbital norms provide results of similar quality

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The semiclassical Wigner treatment of Brown and Heller [J. Chem. Phys. 1981, 75, 186] is applied to direct triatomic (or triatomic-like polyatomic) photodissociations with the aim of accurately predicting final state distributions at relatively low computational cost, and having available a powerful interpretative tool. For the first time, the treatment takes rotational motions into account. The proposed formulation closely parallels the quantum description as far as possible. An approximate version is proposed, which is still accurate while numerically much more efficient. In addition to being weighted by usual vibrational Wigner distributions, final phase space states appear to be weighted by new rotational Wigner distributions. These densities have remarkable structures clearly showing that classical trajectories most contributing to rotational state j are those reaching the products with a rotational angular momentum close to [j(j + 1)](1/2) (in ℏ units). The previous methods involve running trajectories from the reagent molecule onto the products. The alternative backward approach [L. Bonnet, J. Chem. Phys., 2010, 133, 174108], in which trajectories are run in the reverse direction, is shown to strongly improve the numerical efficiency of the most rigorous method in addition to being state-selective, and thus, ideally suited to the description of state-correlated distributions measured in velocity imaging experiments. The results obtained by means of the previous methods are compared with rigorous quantum results in the case of Guo's triatomic-like model of methyl iodide photodissociation [J. Chem. Phys., 1992, 96, 6629] and close agreement is found. In comparison, the standard method of Goursaud et al. [J. Chem. Phys., 1976, 65, 5453] is only semi-quantitative.