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Bressan, Giovanni 
ORCID: https://orcid.org/0000-0001-7801-8495 and van Thor, Jasper J.
(2021)
Theory of two-dimensional spectroscopy with intense laser fields.
The Journal of Chemical Physics, 154 (24).
ISSN 0021-9606
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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.
| Item Type: | Article |
|---|---|
| Additional Information: | Funding information: G.B. and J.J.v.T. acknowledge support from The Leverhulme Trust under Award No. RPG-2018-372. |
| Uncontrolled Keywords: | physics and astronomy(all),physical and theoretical chemistry ,/dk/atira/pure/subjectarea/asjc/3100 |
| Faculty \ School: | Faculty of Science > School of Chemistry |
| Related URLs: | |
| Depositing User: | LivePure Connector |
| Date Deposited: | 14 Jul 2021 00:29 |
| Last Modified: | 23 Oct 2022 02:39 |
| URI: | https://ueaeprints.uea.ac.uk/id/eprint/80552 |
| DOI: | 10.1063/5.0051435 |
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