2D electronic-vibrational spectroscopy with classical trajectories
Kritanjan Polley1, Roger F Loring1
1Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, USA.
The Journal of Chemical Physics
|June 1, 2022
Summary
This study introduces a computational method to analyze molecular interactions using two-dimensional electronic-vibrational (2DEV) spectroscopy. The approach accurately models complex electron-nuclear dynamics and vibrational energy flow in molecules.
Area of Science:
- Physical Chemistry
- Spectroscopy
- Computational Chemistry
Background:
- Two-dimensional electronic-vibrational (2DEV) spectroscopy offers insights into electron-nuclear interactions.
- Understanding these interactions is crucial for molecular dynamics and energy transfer studies.
Purpose of the Study:
- To develop and validate a computational approach for calculating 2DEV spectra.
- To investigate electron-nuclear and vibronic couplings in molecular systems.
Main Methods:
- Application of the trajectory-based semiclassical optimized mean trajectory (TSOMT) approach.
- Computation of 2DEV spectra for a model system with excitonically coupled electronic states and vibronically coupled modes.
- Inclusion of bath coupling to simulate vibrational population redistribution.
Main Results:
- The computed 2DEV spectra accurately reproduce benchmark calculations.
- Observed lineshapes and delay-time dynamics align with theoretical predictions.
- The method successfully distinguishes contributions from different spectroscopic pathways.
Conclusions:
- The TSOMT approach is a reliable tool for simulating 2DEV spectra.
- This method provides a detailed understanding of electron-nuclear dynamics and vibrational energy flow.
- The findings facilitate the interpretation of complex spectroscopic data in molecular systems.
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