Nonstationary Electronic States and Site-Selective Reactivity
摘要：
An efficient route to the site-selective reactivity of electronically excited states of multicentered molecules is discussed. In the first stage the migration of the electronic excitation occurs. This can operate over an extensive range without extensive draining of energy into the nuclear frame. Only in a second stage, once the optimal site has been reached, does the excess energy become available for bond breaking or isomerization at the new, optimal, site. This two-stage mechanism, where electronic excitation (or the charge) is the scout, avoids the pitfall of conventional large molecule kinetics. (In that view, known as the quasi equilibrium theory, the electronic excitation is first converted to nuclear modes. But then there are so many available vibrational states that the probability for the excitation energy to become localized at the necessary site is too small and the resulting reaction rate is too slow.) By confining the site search to the electronic manifold, it becomes a highly efficient proc...
展开
DOI：
10.1021/jp9715742
被引量：
年份：
2007
相似文献
参考文献
引证文献
引用走势
站内活动
辅助模式
引用
文献可以批量引用啦~
欢迎点我试用！
