Resolving competing conical intersection pathways: time-resolved X-ray absorption spectroscopy of trans-1,3-butadiene
Issaka Seidu1, Simon P Neville1, Ryan J MacDonell2
1National Research Council Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6, Canada. Michael.Schuurman@uottawa.ca.
Time-resolved X-ray absorption spectroscopy (TRXAS) can distinguish competing molecular pathways after photoexcitation. This technique probes distinct electronic structures, enabling control over excited-state dynamics.
Area of Science:
- Physical Chemistry
- Molecular Dynamics
- Spectroscopy
Background:
- Time-resolved X-ray absorption spectroscopy (TRXAS) probes molecular dynamics after photoexcitation.
- Conical intersections (CIs) are crucial in excited-state molecular dynamics.
- Resolving competing pathways involving multiple CIs is challenging.
Purpose of the Study:
- Demonstrate TRXAS's capability to resolve competing excited-state non-adiabatic dynamics.
- Utilize 1,3-butadiene as a model system to show pathway discernment.
- Highlight XAS's potential for controlling molecular dynamics via chemical substitution.
Main Methods:
- Theoretical studies of photo-excited molecules.
- Application of time-resolved X-ray absorption spectroscopy (TRXAS).
- Analysis of excited-state wave packet dynamics through conical intersections.
Main Results:
- TRXAS can differentiate competing dynamical pathways in photo-excited molecules.
- Distinct electronic structures associated with different CIs yield unique XAS signals.
- 1,3-butadiene shows branching between polarized and radicaloid pathways, resolvable by TRXAS.
Conclusions:
- TRXAS is a powerful tool for resolving competing channels in excited-state non-adiabatic dynamics.
- The technique can discern different electronic structures during CI passage.
- Core-level spectroscopy offers prospects for controlling molecular dynamics through chemical modification.
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