RT Journal Article
T1 Non-adiabatic photodissociation dynamics of vinyl iodide from nσ* and nπ* transitions
A1 Murillo Sánchez, Marta Luisa
A1 Marggi Poullaín, Sonia
A1 Limao-Vieira, Paulo
A1 Zanchet, Alexandre
A1 De Oliveira, Nelson
A1 Gonzalez Vazquez, Jesus
A1 Bañares Morcillo, Luis
AB The photodissociation dynamics of vinyl iodide upon photoexcitation at 199.2 and 200 nm are investigated in a joint theoretical and experimental study. The gas-phase absorption spectrum measured by Fourier transform spectroscopy along with the use of synchrotron radiation is reported and a reassignment of the excited electronic states responsible for the absorption at the energy range of interest is proposed. Femtosecond time-resolved velocity map imaging in conjunction with resonance enhanced multiphoton ionization detection of the I(2P3/2) and I*(2P1/2) photofragments have been carried out. The experimental results are discussed in view of high-level ab initio calculations including potential energy curves and semiclassical dynamics. Three conical intersections (CIs) governing the dynamics are identified in a search for stationary points using spin–orbit gradients. Based on these results, a complete picture of the photodissociation dynamics of vinyl iodide is obtained. Photoexcitation at 200 nm, associated with a nI(⊥)σ* transition, leads to a fast dissociation occurring in a repulsive potential energy surface, which is mediated by a CI with a low-lying excited electronic state. This mechanism resembles the typical dissociation of alkyl iodides in the first absorption A-band. In contrast, one-photon excitation at 199.2 nm into a well-defined vibronic structure of the absorption spectrum is assigned to a nI(‖)π* transition. The subsequent dissociation dynamics from that state features an ultrafast electronic predissociation with sub-200 femtosecond reaction time. State-switching at a first CI with a low-lying electronic state governing the mechanism involves states of completely different character, occurring in less than 20 fs. This remarkably fast process takes place through an initial stretch of the C[double bond, length as m-dash]C bond, followed by a C–I elongation with subsequent vibrational activity in the C[double bond, length as m-dash]C stretch mode.
PB Royal Society of Chemistry
YR 2025
FD 2025-01-18
LK https://hdl.handle.net/20.500.14352/124056
UL https://hdl.handle.net/20.500.14352/124056
LA eng
NO Murillo-Sánchez, Marta L., et al. «Non-Adiabatic Photodissociation Dynamics of Vinyl Iodide from Nσ* and Nπ* Transitions». Physical Chemistry Chemical Physics, vol. 27, n.o 16, 2025, pp. 8354-67.
NO Ministerio de Ciencia, Innovación y Universidades (España)
DS Docta Complutense
RD 1 ene 2026