Multidimensional Hydrogen Bond Dynamics in Salicylaldimine: Coherent Nuclear Wave Packet Motion versus Intramolecular Vibrational Energy Redistribution
Multidimensional Hydrogen Bond Dynamics in Salicylaldimine: Coherent Nuclear Wave Packet Motion versus Intramolecular Vibrational Energy Redistribution
复制标题
水杨醛亚胺中的多维氢键动力学：相干核波包运动与分子内振动能量重新分布
DOI：
10.1021/jp035688r
复制
发表时间：
2003
影响因子：
2.9
通讯作者：
O. Kühn
中科院分区：
文献类型：
--
作者：
M. Petković;O. Kühn
讨论了水杨醛二胺分子在超快红外激光激发下的多维波包动力学。采用非绝热表象中的七维笛卡尔反应面哈密顿量，包括对面内氢气运动影响最大的五个骨架简正模。对于含时薛定谔方程的数值解，采用了多组态含时Hartree方法。在OH-弯曲基态跃迁激发后观察到相干波包动力学，而与伸缩跃迁的强非简谐耦合导致分子内振动能量在约700fs的时间尺度上重新分配。
The multidimensional wave packet dynamics of salicylaldimine following ultrafast infrared laser excitation of the OH-bending and -stretching vibrations is discussed. A seven-dimensional Cartesian reaction surface Hamiltonian in the diabatic representation is employed comprising the five skeleton normal modes which have the greatest influence on the in-plane hydrogen motion. For the numerical solution of the time-dependent Schrodinger equation the multiconfiguration time-dependent Hartree method is used. Coherent wave packet dynamics is observed after excitation of the OH-bending fundamental transition, whereas stiong anharmonic mode couplings to the stretching transition cause intramolecular vibrational energy redistribution on a time scale of about 700 fs.