HSS和HOO反应机理的研究
Studies on the reaction mechanism of HSS and HOO

本文采用G2M(CC5)//B3PW91/6-311+G(3df,2p)方法研究了HSS和HOO反应机理. 结果表明，HSS与HOO反应主要存在4条通道，分别生成产物P1(H？？？？2？？O+SSO), P2(H？？？？2？？O？？？？2？？+？？？？1？？S？？？？2？？), P3(H？？？？2？？S？？？？2？？+？？？？1？？O？？？？2？？)和P4(H？？？？2？？+SSOO)，主通道为生成P1(H？？？？2？？O+SSO)的通道，其表观活化能为-124？？31 kJ?mol？？？？-1？？. 根据传统过渡态理论结合隧道效应校正，计算了各个通道在298~1000 K温度范围内的表观速率常数？？k？觯？发现产物P1(H？？？？2？？O+SSO)主产物，总速率常数呈现负温度系数效应. 此外，理论预测了稳定物种的生成焓(ΔfH？？？？e？？298K)，计算结果与实验较为接近.
The mechanism for the reaction of HSS with HOO is investigated by using G2M(CC5)//B3PW91/6-311+G(3df,2p). Four possible reaction channels〓for the formation of P1(H？？？？2？？O+SSO), P2(H？？？？2？？O？？？？2？？+？？？？1？？S？？？？2？？), P3(H？？？？2？？S？？？？2？？+？？？？1？？O？？？？2？？) and P4(H？？？？2？？+SSOO) are found in the reaction of HOO and HSS. The result indicates that the main channel is the formation of P1(H？？？？2？？O+SSO) with the apparent activation energy of -124？？31 kJ?mol？？？？-1？？. Rate constants of all the channels over the temperature range of 298~1000 K are evaluated using the transition state theory. Formation enthalpies (ΔfH？？？？e？？298K) of all the minima are predicted, which are in good agreement with the available experimental values