Quantum dynamics of the CH3 fragment:: A curvilinear coordinate system and kinetic energy operators

A curvilinear coordinate system for AB(3) fragments is given. The corresponding exact kinetic energy operator is derived and a series of simpler, progressively more approximate kinetic energy operators are suggested. The operators are tailored for quantum dynamics simulations using the multiconfigurational time-dependent Hartree approach. It is outlined how these fragment coordinates can be utilized to set up coordinate systems for larger systems such as AB(3)C or AB(3)CD. Calculations of the vibrational levels of CH3 and quantum dynamics studies investigate the accuracy of the different kinetic energy operators suggested. (c) 2007 American Institute of Physics.