Theory of two-dimensional spectroscopy with intense laser fields
File(s)JCP21-AR-CMDS2021-01126.pdf (787.44 KB)
Accepted version
Author(s)
Bressan, Giovanni
van Thor, Jasper J
Type
Journal Article
Abstract
Two-dimensional vibrational and electronic spectroscopic observables of isotropically oriented molecular samples in solution are sensitive to laser field intensities and polarization. The third-order response function formalism predicts a signal that grows linearly with the field strength of each laser pulse, thus lacking a way of accounting for non-trivial intensity-dependent effects, such as saturation and finite bleaching. An analytical expression to describe the orientational part of the molecular response, which, in the weak-field limit, becomes equivalent to a four-point correlation function, is presented. Such an expression is evaluated for Liouville-space pathways accounting for diagonal and cross peaks for all-parallel and cross-polarized pulse sequences, in both the weak- and strong-field conditions, via truncation of a Taylor series expansion at different orders. The results obtained in the strong-field conditions suggest how a careful analysis of two-dimensional spectroscopic experimental data should include laser pulse intensity considerations when determining molecular internal coordinates.
Date Issued
2021-06-28
Date Acceptance
2021-06-01
Citation
The Journal of Chemical Physics, 2021, 154 (24), pp.1-10
ISSN
0021-9606
Publisher
AIP Publishing
Start Page
1
End Page
10
Journal / Book Title
The Journal of Chemical Physics
Volume
154
Issue
24
Copyright Statement
© 2021 Author(s). This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in J. Chem. Phys. 154, 244111 (2021); https://doi.org/10.1063/5.0051435
Sponsor
The Leverhulme Trust
Identifier
https://aip.scitation.org/doi/10.1063/5.0051435
Grant Number
RPG-2018-372
Subjects
02 Physical Sciences
03 Chemical Sciences
09 Engineering
Chemical Physics
Publication Status
Published
Date Publish Online
2021-06-28