Si(~3P_g)+CO(X^1∑^+)体系的平行络合竞争动力学

The parallel complex reactions dynamics of Si(~3P_g)+CO(X^1∑^+)

使用经典轨迹法研究了平行络合反应Si(3Pg)+CO(X1∑+,V=0、1,J=0)→SiCO(X3∑-)或SiOC(X3∑-).该两个反应均无阈能,络合物寿命较长,一般在2.0×10-12sec左右,有效络合反应能区较窄(初始相对碰撞平动能Et≤37.6560 kJ.mol-1).当CO(X1∑+)的V=0或1时,较高稳定性的SiCO(X3∑-)在低能区(Et<12.5520 kJ.mol-1)均具有相对明显的优势,空间位阻因素起决定作用;在中能区(12.5520≤Et≤37.6560 kJ.mol-1),空间位阻因素减弱,能量因素加强,两者的反应速率接近相等;在高能区(Et>37.6560 kJ.mol-1),两个络合反应几乎不发生.

The parallel complex reactions Si（^3Pg）＋CO（X^1∑^＋,V=0、1,J=0）→SiCO（X^3∑^-） or SiOC（X^3∑^-） have been studied using the classical trajectory method. There aren＇t threshold energies in the two reactions. The lifetimes of the two complexes SiCO（X^3∑^ - ）and SiOC（X^3∑^- ） are longer to be about 2.0 × 10^-12 see and the effective energy regions of the two complex reactions are relatively narrow, i.e., Et≤ 37. 6560 kJ. mol^- 1. When the initial translation energy Et 〈 12. 5520 kJ. mol^- 1, SiCO（ X ^3∑^ - ） is the superior product which is mainly determinated by the spatial steric effect. In the middle energy region, that is, 12.5520≤Et≤37. 6560 kJ. mo1^-1, their reaction rates are almost the same because of the strengthen of the structural transformation and dissociation of the two complexes caused by the increase of energies. The two parallel complex reactions almost haven＇ t happened because of the dissociations of the two complex when Et 〉 37. 6560 kJ. mol^- 1.