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Updated: Jul 14, 2025
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Ultrafast Time-resolved Near-IR Stimulated Raman Measurements of Functional π-conjugate Systems
Published on: February 10, 2020
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Coupled Cluster Simulation of Impulsive Stimulated X-ray Raman Scattering
Alice Balbi1, Andreas S Skeidsvoll2, Henrik Koch1,2
1Scuola Normale Superiore, Piazza dei Cavalieri, 7, I-56126 Pisa, Italy.
The Journal of Physical Chemistry. A
|October 9, 2023
Summary
Time-dependent equation-of-motion coupled cluster (TD-EOM-CC) simulations reveal that ultrashort laser pulses can efficiently transfer electronic populations to valence states via Raman scattering. This process, analyzed using the core-valence separation approximation, shows sensitivity to pulse parameters.
Area of Science:
- Computational Chemistry
- Quantum Dynamics
- Spectroscopy
Background:
- Impulsive stimulated X-ray Raman scattering (ISXRS) is a powerful technique for probing electronic structure.
- Accurate theoretical modeling is crucial for understanding ISXRS dynamics.
- Time-dependent equation-of-motion coupled cluster (TD-EOM-CC) offers a robust framework for such simulations.
Purpose of the Study:
- To simulate ISXRS of ultrashort laser pulses on various molecules (Ne, CO, pyrrole, p-aminophenol).
- To investigate the transfer of electronic population to core- and valence-excited states.
- To analyze the influence of pulse characteristics and model parameters on population transfer.
Main Methods:
- Employed time-dependent equation-of-motion coupled cluster (TD-EOM-CC) theory.
- Utilized the core-valence separation (CVS) approximation for simplified core-excited state calculations.
- Calculated electronic population transfer for varying numbers of excited states and pulse parameters (polarization, frequency).
Main Results:
- Gaussian laser pulses demonstrated significant electronic population transfer to valence states via the Raman process.
- Population transfer exhibited sensitivity to the number of included excited states and pulse properties.
- Time-dependent electronic density analysis for p-aminophenol supported the role of localized core excitations.
Conclusions:
- TD-EOM-CC with CVS approximation is effective for simulating ISXRS dynamics.
- ISXRS can be utilized to rapidly generate valence electronic wavepackets.
- The study highlights the potential of ISXRS for probing molecular electronic structure and dynamics.
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