Issue 3, 2018

The effect of solvent relaxation in the ultrafast time-resolved spectroscopy of solvated benzophenone

Abstract

Benzophenone (BP) despite its relatively simple molecular structure is a paradigmatic sensitizer, featuring both photocatalytic and photobiological effects due to its rather complex photophysical properties. In this contribution we report an original theoretical approach to model realistic, ultra-fast spectroscopy data, which requires describing intra- and intermolecular energy and structural relaxation. In particular we explicitly simulate time-resolved pump–probe spectra using a combination of state-of-the art hybrid quantum mechanics/molecular mechanics dynamics to treat relaxation and vibrational effects. The comparison with experimental transient absorption data demonstrates the efficiency and accuracy of our approach. Furthermore the explicit inclusion of the solvent, water for simulation and methanol for experiment, allows us, despite the inherent different behavior of the two, to underline the role played by the H-bonding relaxation in the first hundreds of femtoseconds after optical excitation. Finally we predict for the first time the two-dimensional electronic spectrum (2DES) of BP taking into account the vibrational effects and hence modelling partially symmetric and asymmetric ultrafast broadening.

Graphical abstract: The effect of solvent relaxation in the ultrafast time-resolved spectroscopy of solvated benzophenone

Supplementary files

Article information

Article type
Paper
Submitted
04 Dec. 2017
Accepted
15 Janv. 2018
First published
15 Janv. 2018

Photochem. Photobiol. Sci., 2018,17, 323-331

The effect of solvent relaxation in the ultrafast time-resolved spectroscopy of solvated benzophenone

E. Zvereva, J. Segarra-Martí, M. Marazzi, J. Brazard, A. Nenov, O. Weingart, J. Léonard, M. Garavelli, I. Rivalta, E. Dumont, X. Assfeld, S. Haacke and A. Monari, Photochem. Photobiol. Sci., 2018, 17, 323 DOI: 10.1039/C7PP00439G

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Spotlight

Advertisements