Stark control of multiphoton ionization through Freeman resonances in alkyl iodides

Multiphoton ionization (MPI) of alkyl iodides (RI, R = CnH2n+1, n = 1–4) has been investigated with femtosecond laser pulses centered at 800 and 400 nm along with photoelectron imaging detection. In addition, the ultraviolet (UV)–vacuum ultraviolet (VUV) absorption spectra of gas-phase RIs have been...

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Detalles Bibliográficos
Autores: Casasús, Ignacio M., Corrales Castellanos, María Eugenia, Murillo-Sánchez, Marta L., Marggi Poullain, Sonia, Oliveira, Nelson de, Limão-Vieira, Paulo, Bañares, Luis
Tipo de recurso: artículo
Fecha de publicación:2023
País:España
Institución:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/710467
Acceso en línea:http://hdl.handle.net/10486/710467
https://dx.doi.org/10.1063/5.0161628
Access Level:acceso abierto
Palabra clave:Photoelectron imaging
Photoionization,
Stark effect
Rydberg states
Física
Química
Descripción
Sumario:Multiphoton ionization (MPI) of alkyl iodides (RI, R = CnH2n+1, n = 1–4) has been investigated with femtosecond laser pulses centered at 800 and 400 nm along with photoelectron imaging detection. In addition, the ultraviolet (UV)–vacuum ultraviolet (VUV) absorption spectra of gas-phase RIs have been measured in the photon energy range of 5–11 eV using the VUV Fourier transform spectrometer at the VUV DESIRS beamline of the synchrotron SOLEIL facility. The use of high-laser-field strengths in matter–radiation interaction generates highly non-linear phenomena, such as the Stark shift effect, which distorts the potential energy surfaces of molecules by varying both the energy of electronic and rovibrational states and their ionization energies. The Stark shift can then generate resonances between intermediate states and an integer number of laser photons of a given wavelength, which are commonly known as Freeman resonances. Here, we study how the molecular structure of linear and branched alkyl iodides affects the UV–VUV absorption spectrum, the MPI process, and the generation of Freeman resonances. The obtained results reveal a dominant resonance in the experiments at 800 nm, which counter-intuitively appears at the same photoelectron kinetic energy in the whole alkyl iodide series. The ionization pathways of this resonance strongly involve the 6p( 2 E3/2) Rydberg state with different degrees of vibrational excitation, revealing an energy compensation effect as the R-chain complexity increases