Ab Initio Modeling Of Ultrafast Nonlinear Optical Signals In Molecular Systems Involving Electronic Transitions

Thurston, Richard

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https://hdl.handle.net/2142/116961 Copy

Description

Title

Ab Initio Modeling Of Ultrafast Nonlinear Optical Signals In Molecular Systems Involving Electronic Transitions

Author(s)

Thurston, Richard

Contributor(s)

• Slaughter, Daniel S.
• Tan, Liang Z.
• Weber, Thorsten

Issue Date

2022-06-21

Keyword(s)

Theory and Computation

Abstract

The observation of ultrafast time-resolved molecular dynamics after electronic excitation often relies on the measurement and interpretation of nonlinear optical signals. These signals can be very challenging to interpret without the aid of a theoretical model. A common approach to understand these signals is by using parameterized semi-empirical models that describe the specific process under study. These methods can be very useful and are very flexible but finding appropriate parameter values can be challenging, and the physical interpretation of these parameters can be ambiguous. Ab initio calculations can reduce the number of free parameters. However, available quantum chemistry packages like Dalton, QChem, and others, typically report frequency domain information, and tracking the evolution of the target usually requires the mapping of time onto a nuclear reaction coordinate which may not be observable. Here we present an ab initio approach to modeling time domain ultrafast nonlinear optical signals that addresses these issues by using the Dalton quantum chemistry package to parameterize a general N-level model which is then evaluated using a Liouville space representation. We compare these results to recent Ultrafast Transient Polarization Spectroscopy measurements of nitrobenzene. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences of the U.S. Department of Energy under Contract no. DE-AC02-05CH11231.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

eng

Handle URL

https://hdl.handle.net/2142/116961&&

DOI

https://doi.org/10.15278/isms.2022.TL05

Copyright and License Information

Copyright 2022 held by the authors

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