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Effective Inclusion of Mechanical and Electrical Anharmonicity in Excited Electronic States: VPT2-TDDFT Route

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journal contribution
posted on 28.04.2017, 00:00 authored by Franco Egidi, David B. Williams-Young, Alberto Baiardi, Julien Bloino, Giovanni Scalmani, Michael J. Frisch, Xiaosong Li, Vincenzo Barone
We present a reliable and cost-effective procedure for the inclusion of anharmonic effects in excited-state energies and spectroscopic intensities by means of second-order vibrational perturbation theory. This development is made possible thanks to a recent efficient implementation of excited-state analytic Hessians and properties within the time-dependent density functional theory framework. As illustrated in this work, by taking advantage of such algorithmic developments, it is possible to perform calculations of excited-state infrared spectra of medium-large isolated molecular systems, with anharmonicity effects included in both the energy and property surfaces. We also explore the use of this procedure for the inclusion of anharmonic effects in the simulation of vibronic bandshapes of electronic spectra and compare the results with previous, more approximate models.