Two-dimensional electronic-vibrational (2DEV) spectra have the capacity to probe electron–nuclear interactions in molecules by measuring correlations between initial electronic excitations and vibrational transitions at a later time. The trajectory-based semiclassical optimized mean trajectory approach is applied to compute 2DEV spectra for a system with excitonically coupled electronic excited states vibronically coupled to a chromophore vibration. The chromophore mode is in turn coupled to a bath, inducing redistribution of vibrational populations. The lineshapes and delay-time dynamics of the resulting spectra compare well with benchmark calculations, both at the level of the observable and with respect to contributions from distinct spectroscopic processes.
2D electronic-vibrational spectroscopy with classical trajectories
Note: This paper is part of the JCP Special Topic on Photosynthetic Light-Harvesting and Energy Conversion.
Kritanjan Polley, Roger F. Loring; 2D electronic-vibrational spectroscopy with classical trajectories. J. Chem. Phys. 28 May 2022; 156 (20): 204110. https://doi.org/10.1063/5.0090868
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