Conical intersection and coherent vibrational dynamics in alkyl iodides captured by attosecond transient absorption spectroscopy

Chang, Kristina F.; Wang, Han; Poullain, Sonia M.; González-Vázquez, Jesús; Bañares, Luis; Prendergast, David; Neumark, Daniel M.; Leone, Stephen R.

doi:10.1063/5.0086775

Title: Conical intersection and coherent vibrational dynamics in alkyl iodides captured by attosecond transient absorption spectroscopy

Journal Article · Fri Mar 18 00:00:00 EDT 2022 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0086775· OSTI ID:1855892

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The photodissociation dynamics of alkyl iodides along the C–I bond are captured by attosecond extreme-ultraviolet (XUV) transient absorption spectroscopy employing resonant ∼20 fs UV pump pulses. The methodology of previous experiments on CH3I [Chang et al., J. Chem. Phys. 154, 234301 (2021)] is extended to the investigation of a C–I bond-breaking reaction in the dissociative A-band of C2H5I, i-C3H7I, and t-C4H9I. Probing iodine 4d core-to-valence transitions in the XUV enables one to map wave packet bifurcation at a conical intersection in the A-band as well as coherent vibrations in the ground state of the parent molecules. Analysis of spectroscopic bifurcation signatures yields conical intersection crossing times of 15 ± 4 fs for CH3I, 14 ± 5 fs for C2H5I, and 24 ± 4 fs for i-C3H7I and t-C4H9I, respectively. Observations of coherent vibrations, resulting from a projection of A-band structural dynamics onto the ground state by resonant impulsive stimulated Raman scattering, indirectly reveal multimode C–I stretch and CCI bend vibrations in the A-bands of C2H5I, i-C3H7I, and t-C4H9I.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1855892

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Vol. 156 Journal Issue: 11; ISSN 0021-9606

Publisher:: American Institute of PhysicsCopyright Statement

Country of Publication:: United States

Language:: English

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