Manthe Uwe
Theoretische Chemie, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25, 33615 Bielefeld, Germany.
J Chem Phys. 2008 Apr 28;128(16):164116. doi: 10.1063/1.2902982.
The multiconfigurational time-dependent Hartree (MCTDH) approach facilitates multidimensional quantum dynamics calculations by representing the wavepacket in an optimal set of time-dependent basis functions, called single-particle functions. Choosing these single-particle functions to be themselves multidimensional wavefunctions which are represented using a MCTDH representation, a multilayer MCTDH scheme has been constructed and used for quantum dynamics calculations treating up to 1000 degrees of freedom rigorously [Wang and Thoss, J. Chem. Phys. 199, 1289 (2003)]. The present work gives a practical scheme which facilitates the application of the multilayer MCTDH approach, which previously has only been employed to study systems described by model-type Hamiltonians, to molecular systems described by more complicated Hamiltonians and general potential energy surfaces. A multilayer extension of the correlation discrete variable representation (CDVR) scheme employed in MCTDH calculations studying quantum dynamics on general potential energy surfaces is developed and tested in a simple numerical application. The resulting multilayer MCTDH/CDVR approach might offer a perspective to rigorously describe the quantum dynamics of larger polyatomic systems.
多组态含时哈特里（MCTDH）方法通过在一组最优的含时基函数（称为单粒子函数）中表示波包，来推动多维量子动力学计算。将这些单粒子函数本身选为使用MCTDH表示法表示的多维波函数，构建了一种多层MCTDH方案，并将其用于严格处理多达1000个自由度的量子动力学计算[Wang和Thoss，《化学物理杂志》199，1289（2003）]。目前的工作给出了一种实用方案，有助于将多层MCTDH方法应用于分子体系，该方法此前仅用于研究由模型型哈密顿量描述的体系，而现在应用于由更复杂的哈密顿量和一般势能面描述的分子体系。在一个简单的数值应用中，开发并测试了MCTDH计算中用于研究一般势能面上量子动力学的相关离散变量表示（CDVR）方案的多层扩展。由此产生的多层MCTDH/CDVR方法可能为严格描述更大的多原子体系的量子动力学提供一个视角。
