Vibrational Sampling and Solvent Effects on the Electronic Structure of the Absorption Spectrum of 2-Nitronaphthalene.

Abstract

The influence of vibrational motion on electronic excited state properties is investigated for the organic chromophore 2-nitronaphtalene in methanol. Specifically, the performance of two vibrational sampling techniques - Wigner sampling and sampling from an ab initio molecular dynamics trajectory- is assessed, in combination with implicit and explicit solvent models. The effects of the different sampling/solvent combinations on the energy and electronic character of the absorption bands are analyzed in terms of charge transfer and exciton size, computed from the electronic transition density. The absorption spectra obtained using sampling techniques and its underlying properties are compared to those of the electronic excited states calculated at the Franck-Condon equilibrium geometry. It is found that the absorption bands of the vibrational ensembles are red-shifted compared to the Franck-Condon bright states, and this red-shift scales with the displacement from the equilibrium geometry. Such displacements are found larger and better described when using ensembles from the harmonic Wigner distribution than snapshots from the molecular dynamics trajectory. Particularly relevant is the torsional motion of the nitro group that quenches the charge transfer character of some of the absorption bands. This motion, however, is better described in the molecular dynamics trajectory. Thus, none of the vibrational sampling approaches can satisfactorily capture all important aspects of the nuclear motion. The inclusion of solvent also red-shifts the absorption bands with respect to the gas phase. This red-shift scales with the charge-transfer character of the bands and is found larger for the implicit than for the explicit solvent model. The advantages and drawbacks of the different sampling and solvent models are discussed to guide future research on the calculation of UV-vis spectra of nitroaromatic compounds.