- 作者: 邱智宏 ; 何嘉仁
- 作者服務機構: 台灣師範大學化學系
- 中文摘要: The reactants, ion-dipole complexes, transition states, and products for the proton transfer reactions HBCOH/sup +/+OCXH.arrr.HBCO+/sup +/HOCXH optimized at the SCF/4-31G/sup */ level of theory for B, X=F, Cl, H, CH/sub 3/, CH/sub 2/Cl, CHCl/sub 2/ and CCl/sub 3/ are studied. The intrinsic barrier .DELTA.E/sub BX//sup #/ correlates with the degree of the O-O bond contraction in the transition structure. Both intrinsic and overall barriers can be predicted with the aid of Marcus theory. Progressive degrees of chlorination of the alkyl group in B produce decreases in the barrier to proton transfer from HBCOH/sup +/ to OCXH and increases in the reverse transfer barriers. These changes can be quantitatively reproduced by the Marcus equation for all systems.
- 英文摘要: --
- 中文關鍵字: Ab Initio Method; Proton Transfer Barrier; Marcus Theory
- 英文關鍵字: 從頭計算方法;質子轉移障壁;Marcus理論