We present a computational strategy to simulate the absorption lineshape of a molecule embedded in a complex environment by using a polarizable QM/MM approach. This strategy is presented in two alternative formulations, one based on a molecular dynamics simulation of the structural fluctuations of the system and the other using normal modes and harmonic frequencies calculated on optimized geometries. The comparison for the case of a chromophore within a strongly inhomogeneous and structured environment, namely the intercalation pocket of DNA, shows that the MD-based approach is able to reproduce the experimental spectral bandshape. In contrast, the static approach overestimates the vibronic coupling, resulting in a much broader band.

The modeling of the absorption lineshape for embedded molecules through a polarizable QM/MM approach

Cupellini, Lorenzo;Mennucci, Benedetta
2018-01-01

Abstract

We present a computational strategy to simulate the absorption lineshape of a molecule embedded in a complex environment by using a polarizable QM/MM approach. This strategy is presented in two alternative formulations, one based on a molecular dynamics simulation of the structural fluctuations of the system and the other using normal modes and harmonic frequencies calculated on optimized geometries. The comparison for the case of a chromophore within a strongly inhomogeneous and structured environment, namely the intercalation pocket of DNA, shows that the MD-based approach is able to reproduce the experimental spectral bandshape. In contrast, the static approach overestimates the vibronic coupling, resulting in a much broader band.
2018
Loco, Daniele; Jurinovich, Sandro; Cupellini, Lorenzo; Menger, MAXIMILIAN FRIEDRICH SEBASTIAN JOHANNES; Mennucci, Benedetta
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11568/941994
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