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Theoretical Study on the Spectroscopic Properties of CO 3 .− . n H 2 O Clusters: Extrapolation to Bulk
Author(s) -
Pathak Arup K.,
Mukherjee Tulsi,
Maity Dilip K.
Publication year - 2008
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200800429
Subject(s) - chemistry , density functional theory , radiolysis , absorption spectroscopy , perturbation theory (quantum mechanics) , cluster (spacecraft) , coupled cluster , ion , basis set , aqueous solution , ab initio , spectral line , ab initio quantum chemistry methods , analytical chemistry (journal) , atomic physics , molecule , computational chemistry , physics , organic chemistry , chromatography , quantum mechanics , astronomy , computer science , programming language
Vertical detachment energies (VDE) and UV/Vis absorption spectra of hydrated carbonate radical anion clusters, CO 3 .− .n H 2 O (n=1–8), are determined by means of ab initio electronic structure theory. The VDE values of the hydrated clusters are calculated with second‐order Moller–Plesset perturbation (MP2) and coupled cluster theory using the 6‐311++G(d,p) set of basis functions. The bulk VDE value of an aqueous carbonate radical anion solution is predicted to be 10.6 eV from the calculated weighted average VDE values of the CO 3 .− .n H 2 O clusters. UV/Vis absorption spectra of the hydrated clusters are calculated by means of time‐dependent density functional theory using the Becke three‐parameter nonlocal exchange and the Lee–Yang–Parr nonlocal correlation functional (B3LYP). The simulated UV/Vis spectrum of the CO 3 .− .8 H 2 O cluster is in excellent agreement with the reported experimental spectrum for CO 3 .− (aq), obtained based on pulse radiolysis experiments.