Photodetachment and UV–Vis spectral properties of clusters: Extrapolation to bulk

Vertical detachment energy (VDE) and UV–Vis spectra of Cl 2 - · n H 2 O clusters (n = 1–11) are reported based on first principle electronic structure calculations. VDE of the hydrated clusters are calculated following second order Moller–Plesset perturbation (MP2) as well as coupled cluster theory with 6-311++G(d,p) set of basis function. The excess electron in these hydrated clusters is mainly localized over the solute Cl atoms. A linear relationship is obtained for VDE vs. (n + 2.6)−1/3 and bulk VDE of Cl 2 - aqueous solution is calculated as 10.61 eV at CCSD(T) level of theory. UV–Vis spectra of these hydrated clusters are calculated applying CI with single electron (CIS) excitation procedure. Simulated UV–Vis spectra of Cl 2 - · 10 H 2 O cluster is noted to be in excellent agreement with the reported spectra of Cl 2 - (aq) system, λmax for Cl 2 - · 11 H 2 O system is calculated to be red shifted though.