Master equation modeling of water dissociation in small ionic water clusters: Ag+(H2O) n , n = 4-6.
RSC Adv
; 14(31): 22185-22194, 2024 Jul 12.
Article
in En
| MEDLINE
| ID: mdl-39005253
ABSTRACT
We model temperature-dependent blackbody infrared radiative dissociation (BIRD) rate coefficients of Ag+(H2O) n , n = 4-6, a system with loosely bound water molecules. We employ a master equation modeling (MEM) approach with consideration of absorption and emission of blackbody radiation, comparing single and multiple-well descriptions. The unimolecular dissociation rate coefficients are obtained using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory, employing two approaches to model the sum of states in the transition state, the rigid activated complex (RAC) and the phase space limit (PSL) approach. A genetic algorithm is used to find structures of low-lying isomers for the kinetic modeling. We show that the multiple-well MEM approach with PSL RRKM in the All Wells and Transition States Are Relevant (AWATAR) variant provides a reliable description of Ag+(H2O) n BIRD, in agreement with previously published experimental data. Higher-lying isomers contribute significantly to the overall dissociation rate coefficient, underlying the importance of the multiple-well ansatz in which all isomers are treated on the same footing.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
RSC Adv
Year:
2024
Document type:
Article
Country of publication:
United kingdom