Photoinitiation of Gas-Phase SN2 Reactions through the Evans-Polanyi Excited State Surface

摘要

A relatively simple check on whether the I~-/NO_2~- branching ratio indeed reflects partitioning on the ground state surface can be obtained by chemically derivatizing the system. The exothermicity of reaction 2 decreases for the lighter halogens (0. 80, 0.50, and 0.15 eV or I~-, Br~- and Cl~-, respectively) suggesting the the X~-/NO_2~- branching ratio should become smaller along the I/Br/Cl series.