Calculations of Potential Energy Surfaces for the Colliding Reactions of alkaline metal, alkaline-earth metal atoms with alkane, alkene, and their derivatives

• Main Authors: Lai Chien-Liang, 賴建良
• Other Authors: Hung Yu-Ming
• Format: Others
• Language: zh-TW
• Published: 2003
• Online Access: http://ndltd.ncl.edu.tw/handle/00524691203884278323

碩士 === 中國文化大學 === 應用化學研究所 === 91 === In this thesis, we discuss the reactions of the excited alkaline metal atoms (Na* and Li*) colliding with methane (CH4), methyl chloride (CH3Cl), as well as the reactive potential energy surface of reaction of alkaline-earth metal (Be, 21P and Mg, 31P) with ethane (C2H4). Computations were are performed with MOLPRO 2K.2 ab initio quantum calculation software packages using the Multi-configuration Self-consistent Field (MCSCF) method. The CPU time was partially provided by National High Computing Center (NCHC) and by the work stations in our lab. The possible reaction PESs were obtained from the electrmic energy of each designed geometry in the corresponding symmetric pathways (C3V, anti-C3V, C2V), respectively. The information of PESs can help us to get insight understanding of possible intermediates and of reaction conditions. Interestingly, in the collisions of the alkaline metal atoms with alkyl halide, the energy gaps between 2A’ and 1A’ are always found to be large. This indicates a difficult pathway from crossing of different electronic states to obtain the ground state alkaline metal hydride complex. As a result, it is also interesting to discover the reaction pathway of alkaline-earth metal (Be, 21P) with ethane (C2H4). The same conclusion of large energy gap between electronic states (2A’ and 1A’) is given to yield ground state BeH as well. On the contrary, it is a possible pathway with small activation energy in the reaction of Be*+C2H4 →BeH*+C2H3.