The effect of solvent relaxation in the ultrafast time-resolved spectroscopy of solvated benzophenone
File(s)
Accepted version
Author(s)
Type
Journal Article
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.
Date Issued
2018-01-15
Date Acceptance
2018-01-15
Citation
Photochemical & Photobiological Sciences, 2018, 17 (3), pp.323-331
ISSN
1474-905X
Publisher
Royal Society of Chemistry
Start Page
323
End Page
331
Journal / Book Title
Photochemical & Photobiological Sciences
Volume
17
Issue
3
Copyright Statement
© The Royal Society of Chemistry and Owner Societies 2018
Identifier
https://www.ncbi.nlm.nih.gov/pubmed/29383356
Subjects
0306 Physical Chemistry (Incl. Structural)
0601 Biochemistry And Cell Biology
0299 Other Physical Sciences
Organic Chemistry
Publication Status
Published
Coverage Spatial
England