Ridley Trevor, Lawley Kenneth P, Donovan Robert J
School of Chemistry, The University of Edinburgh, West Mains Road, Edinburgh EH9 3JJ, Scotland, United Kingdom.
J Chem Phys. 2009 Mar 28;130(12):124302. doi: 10.1063/1.3098501.
The work presented here extends previous studies of amplified spontaneous emission (ASE) between ion-pair (charge-transfer) states of I(2) and shows that ASE can occur between states correlating with different states of the cation, namely, f0(g)(+)((3)P(0)) and D0(u)(+)((3)P(2)), despite the smaller transition dipole moment between them. A value of 0.34 e A is obtained for the transition dipole under experimental conditions where the f0(g)(+)((3)P(0))-->D0(u)(+)((3)P(2)) ASE is eliminated. No F0(u)(+)((3)P(0))<--f0(g)(+)((3)P(0)) ASE transfer is observed despite the combination of favorable Franck-Condon factors and transition dipoles. The F0(u)(+)((3)P(0))<--f0(g)(+)((3)P(0)) transfer is shown to be purely collisional and a propensity for transfers involving the smallest energy mismatch is observed.
本文所展示的工作扩展了之前关于碘分子（I₂）离子对（电荷转移）态之间放大自发辐射（ASE）的研究，并表明ASE能够在与阳离子不同状态相关的态之间发生，即f0(g)(+)((3)P(0))和D0(u)(+)((3)P(2))，尽管它们之间的跃迁偶极矩较小。在消除f0(g)(+)((3)P(0))-->D0(u)(+)((3)P(2)) ASE的实验条件下，得到跃迁偶极矩的值为0.34 e A。尽管存在有利的弗兰克 - 康登因子和跃迁偶极矩的组合，但未观察到F0(u)(+)((3)P(0))<--f0(g)(+)((3)P(0)) ASE转移。F0(u)(+)((3)P(0))<--f0(g)(+)((3)P(0))转移被证明是纯粹的碰撞过程，并且观察到了涉及最小能量失配的转移倾向。
