Csehi András, Halász Gábor J, Cederbaum Lorenz S, Vibók Ágnes
Department of Theoretical Physics, University of Debrecen, PO Box 400, H-4002 Debrecen, Hungary.
Phys Chem Chem Phys. 2017 Aug 2;19(30):19656-19664. doi: 10.1039/c7cp02164j.
Nonadiabatic effects play a very important role in controlling chemical dynamical processes. They are strongly related to avoided crossings (AC) or conical intersections (CIs) which can either be present naturally or induced by classical laser light in a molecular system. The latter are named as "light-induced avoided crossings" (LIACs) and "light-induced conical intersections" (LICIs). By performing one or two dimensional quantum dynamical calculations LIAC and LICI situations can easily be created even in diatomic molecules. Applying such calculations for the NaI molecule, which is a strongly coupled diatomic in field free case, significant differences between the impact of the LIAC and LICI on the ground state population dynamics were observed. Moreover, obtained results undoubtedly demonstrate that the effect of the LIAC and LICI on the dynamics strongly depends on the intensity and the frequency of the applied laser field as well as the permanent dipole moments of the molecule.
非绝热效应在控制化学动力学过程中起着非常重要的作用。它们与避免交叉(AC)或锥形交叉(CI)密切相关,这些交叉在分子系统中既可以自然存在,也可以由经典激光诱导产生。后者被称为“光诱导避免交叉”(LIAC)和“光诱导锥形交叉”(LICI)。通过进行一维或二维量子动力学计算,即使在双原子分子中也能轻松创建LIAC和LICI情况。将此类计算应用于NaI分子(在无场情况下是强耦合双原子分子),观察到LIAC和LICI对基态布居动力学的影响存在显著差异。此外,所得结果无疑表明,LIAC和LICI对动力学的影响强烈取决于所施加激光场的强度和频率以及分子的永久偶极矩。