Theoretical investigation of intramolecular vibrational energy redistribution in highly excited HFCO.
Theoretical investigation of intramolecular vibrational energy redistribution in highly excited HFCO.
复制标题
高激发 HFCO 中分子内振动能量重新分布的理论研究。
DOI：
10.1063/1.2192499
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发表时间：
2006
期刊：
影响因子：
--
通讯作者：
H. Meyer
中科院分区：
文献类型：
--
作者：
G. Pasin;F. Gatti;C. Iung;H. Meyer
本文模拟了HFCO分子在面外弯曲振动[nnu（6）= 2，4，6，.，18、20]。利用全六维从头算势能，多组态含时Hartree（MCTDH）方法被用来传播相应的六维波包。这项研究强调了高激发态的平面外弯曲模式的稳定性，甚至存在高于解离阈值。更引人注目的是，在动力学的第一步期间，IVR的结构对于从2nu（6）到20 nu（6）的初始激励非常稳定。后一结果与借助于前述论文[Iung和Ribeiro，J.Chem.Phys.121，174 - 105（2005）]中的Davidson算法获得的本征态的分析一致，直到10 nu（6）。本研究可以被认为是对以前调查的补充。本文还展示了如何MCTDH可以用来预测一个强激发系统的动力学行为，并确定相应的高激发态的能量。
The present paper is devoted to the simulations of the intramolecular vibrational energy redistribution (IVR) in HFCO initiated by an excitation of the out-of-plane bending vibration [nnu(6)=2,4,6,...,18,20]. Using a full six-dimensional ab initio potential energy, the multiconfiguration time-dependent Hartree (MCTDH) method was exploited to propagate the corresponding six-dimensional wave packets. This study emphasizes the stability of highly excited states of the out-of-plane bending mode which exist even above the dissociation threshold. More strikingly, the structure of the IVR during the first step of the dynamics is very stable for initial excitations ranging from 2nu(6) to 20nu(6). This latter result is consistent with the analysis of the eigenstates obtained, up to 10nu(6), with the aid of the Davidson algorithm in a foregoing paper [Iung and Ribeiro, J. Chem. Phys. 121, 174105 (2005)]. The present study can be considered as complementary to this previous investigation. This paper also shows how MCTDH can be used to predict the dynamical behavior of a strongly excited system and to determine the energies of the corresponding highly excited states.