Intermolecular Interaction in the H2S鈥揌2 Complex: Molecular Beam Scattering Experiments and Ab-Inito Calculations

详细信息    查看全文

• 作者：Alessio Bartocci ; David Cappelletti ; Fernando Pirani ; Francesco Tarantelli ; Leonardo Belpassi
• 刊名：Journal of Physical Chemistry A
• 出版年：2014
• 出版时间：August 21, 2014
• 年：2014
• 卷：118
• 期：33
• 页码：6440-6450
• 全文大小：513K
• ISSN：1520-5215

文摘

New molecular beam scattering experiments are reported for the H₂S鈥揌₂ system recording, under high angular and velocity resolution conditions, the 鈥済lory鈥?quantum interference in the velocity dependence of the total cross section. The analysis of the experimental data permits the determination, for the first time, of a spherically averaged intermolecular potential for this system. An evaluation of significant cuts of the potential energy surface, obtained by accurate ab initio CCSD(T) calculations using large basis sets, combined with the analysis of the electronic charge displacement accompanying the formation of H₂S鈥揌₂, has been also performed in order to rationalize the experimental findings. A direct comparison with the analogous water鈥揾ydrogen complex (Belpassi, L. et al. J. Am. Chem. Soc. 2010, 132, 13046), investigated with the same experimental conditions and theoretical methodology, brings to light detailed differences in the intermolecular interaction affecting the observables. In particular, it shows the important fact that the charge transfer (CT) component of the interaction plays a minor role in H₂S鈥揌₂, whereas it was found to be a crucial stabilization component of the interaction in water鈥揌₂, determining the potential energy surface anisotropy and the precise location of the energy minima.