A theoretical study of the photochemistry of 1,3-cyclopentadiene and its cyano derivatives bound to a water dimer: Assessing reactivity of ionized clusters and possible photoproducts.
Spectrochim Acta A Mol Biomol Spectrosc
; 320: 124637, 2024 Nov 05.
Article
in En
| MEDLINE
| ID: mdl-38878722
ABSTRACT
We theoretically investigate the photoionization scenarios of molecular complexes involving cyclopentadiene and cyanocyclopentadiene bound to water dimers. Using electronic structure calculations within density-functional theory (DFT) and time dependent DFT (TD-DFT), we explore the potential photochemical pathways following ionization, and determine the charge transfer excitations related to the possible subsequent reactions. Our findings suggest that the investigated photochemical pathways of the hydrated complexes take place in two well-defined ultraviolet regions (i) 8.2-9.5 eV for the cyclic compounds and (ii) 11.2-11.4 eV for the bound water dimer. We quantify how H-bonding effects can influence the photoionization channels. Before forming possible photoproducts, we also examine the regiospecificity of OH addition to 1,3-cyclopentadiene and its cyano derivatives We analyze our results in light of photoionization studies of jet-cooled molecular complexes and possible implications in astrochemical environments.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Spectrochim Acta A Mol Biomol Spectrosc
Journal subject:
BIOLOGIA MOLECULAR
Year:
2024
Document type:
Article
Country of publication:
United kingdom