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Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
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Nonadiabatic phenomena in molecular vibrational polaritons
Tamás Szidarovszky1, Péter Badankó2, Gábor J Halász3
1Institute of Chemistry, ELTE Eötvös Loránd University and MTA-ELTE Complex Chemical Systems Research Group, Pázmány Péter sétány 1/A, H-1117 Budapest, Hungary.
The Journal of Chemical Physics
|February 16, 2021
Summary
Investigating molecular motion in infrared cavities reveals conical intersections in vibrational polaritons. Isotopologue symmetry breaking significantly alters these polaritonic properties, highlighting the need for realistic modeling.
Area of Science:
- Molecular physics
- Quantum optics
- Spectroscopy
Background:
- Nonadiabatic phenomena govern molecular dynamics.
- Vibrational polaritons arise from strong light-matter interactions in cavities.
- Conical intersections (CIs) are crucial in molecular electronic transitions.
Purpose of the Study:
- Investigate nonadiabatic phenomena in molecular rovibrational motion within an infrared cavity.
- Identify and characterize conical intersections between vibrational polaritons.
- Analyze the impact of molecular symmetry on polaritonic properties.
Main Methods:
- Theoretical investigation of molecular systems in optical cavities.
- Analysis of spectral, topological, and dynamic properties of vibrational polaritons.
- Symmetry breaking through isotopic substitution (35Cl to 37Cl) in HCl molecules.
Main Results:
- Conical intersections (CIs) were found between vibrational polaritons, analogous to electronic CIs.
- Nonadiabatic couplings between molecular vibration, rotation, and cavity modes were identified.
- Breaking molecular permutational symmetry via isotopic substitution led to substantial deviations in polaritonic surfaces and dynamics.
Conclusions:
- Vibrational polaritons exhibit spectral, topological, and dynamic fingerprints of nonadiabatic couplings.
- Molecular isotopologue composition significantly influences polaritonic behavior.
- Realistic modeling of polaritonic systems must account for natural isotopic variations.
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