Time resolved photoelectron spectroscopy as a test of electronic structure and nonadiabatic dynamics

Chakraborty, Pratip, Liu, Yusong, McClung, Samuel, Weinacht, Thomas and Matsika, Spiridoula (2021) Time resolved photoelectron spectroscopy as a test of electronic structure and nonadiabatic dynamics. The Journal of Physical Chemistry Letters, 12 (21). pp. 5099-5104. ISSN 1948-7185

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Abstract

We compare different levels of theory for simulating excited state molecular dynamics and use time-resolved photoelectron spectroscopy measurements to benchmark the theory. We perform trajectory surface hopping simulations for uracil excited to the first bright state (ππ*) using three different levels of theory (CASSCF, MRCIS, and XMS-CASPT2) in order to understand the role of dynamical correlation in determining the excited state dynamics, with a focus on the coupling between different electronic states and internal conversion back to the ground state. These dynamics calculations are used to simulate the time-resolved photoelectron spectra. The comparison of the calculated and measured spectra allows us to draw conclusions regarding the relative insights and quantitative accuracy of the calculations at the three different levels of theory, demonstrating that detailed quantitative comparisons of time-resolved photoelectron spectra can be used to benchmark methodology.

Item Type:	Article
Additional Information:	Funding information: The authors gratefully acknowledge the Department of Energy (DOE, Award No. DE-FG02-08ER15983 for Pratip Chakraborty and Spiridoula Matsika and DOE, Award No. DE-FG02-08ER15984 for Yusong Liu, Samuel McClung and Thomas Weinacht) for funding. Part of the computational work was performed using the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation Grant No. ACI-1548562.
Faculty \ School:	Faculty of Science > School of Chemistry, Pharmacy and Pharmacology
Related URLs:	http://www.scopus.com/inward/record.url?...
Depositing User:	LivePure Connector
Date Deposited:	29 Sep 2025 09:30
Last Modified:	25 Oct 2025 16:31
URI:	https://ueaeprints.uea.ac.uk/id/eprint/100479
DOI:	10.1021/acs.jpclett.1c00926

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