The Value of Different Experimental Observables: A Transient Absorption Study of the Ultraviolet Excitation Dynamics Operating in Nitrobenzene.
J Phys Chem A
; 127(31): 6425-6436, 2023 Aug 10.
Article
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| ID: mdl-37494478
ABSTRACT
Excess energy redistribution dynamics operating in nitrobenzene under hexane and isopropanol solvation were investigated using ultrafast transient absorption spectroscopy (TAS) with a 267 nm pump and a 340-750 nm white light continuum probe. The use of a nonpolar hexane solvent provides a proxy to the gas-phase environment, and the findings are directly compared with a recent time-resolved photoelectron imaging (TRPEI) study on nitrobenzene using the same excitation wavelength [L. Saalbach et al., J. Phys. Chem. A 2021, 125, 7174-7184]. Of note is the observation of a 1/e lifetime of 3.5-6.7 ps in the TAS data that was absent in the TRPEI measurements. This is interpreted as a dynamical signature of the T2 state in nitrobenzeneâanalogous to observations in the related nitronaphthalene system, and additionally supported by previous quantum chemistry calculations. The discrepancy between the TAS and TRPEI measurements is discussed, with the overall findings providing an example of how different spectroscopic techniques can exhibit varying sensitivity to specific steps along the overall reaction coordinate connecting reactants to photoproducts.
Texto completo:
1
Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
J Phys Chem A
Asunto de la revista:
QUIMICA
Año:
2023
Tipo del documento:
Article
País de afiliación:
Reino Unido