Ab initio global potential-energy surface for H5(+) --> H3(+) + H2 |
| |
Authors: | Xie Zhen Braams Bastiaan J Bowman Joel M |
| |
Institution: | Cherry L. Emerson Center of Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322. |
| |
Abstract: | An accurate global potential-energy surface (PES) is reported for H5(+) based on more than 100,000 CCSD(T)/aug-cc-pVTZ ab initio energies. This PES has full permutational symmetry with respect to interchange of H atoms and dissociates to H3(+) and H2. Ten known stationary points of H5(+) are characterized and compared to previous ab initio calculations. Quantum diffusion Monte Carlo calculations are performed on the PES to obtain the zero-point energy of H5(+) and the anharmonic dissociation energy (D0) of H5(+) --> H3(+) + H2. The rigorous zero-point state of H4D+ is also calculated and discussed within the context of a strictly classical approach to obtain the branching ratio of the reaction H4D+ --> H3(+) + HD and H2D+ + H2. Such an approach is taken using the PES and critiqued based on the properties of the quantum zero-point state. Finally, a simple procedure for adding the long range-interaction energy is described. |
| |
Keywords: | |
本文献已被 PubMed 等数据库收录! |
|