A rectangular collocation multi-configuration time-dependent Hartree (MCTDH) approach with time-independent points...

We introduce a collocation-based multi-configuration time-dependent Hartree (MCTDH) method that uses more collocation points than basis functions. We call it the rectangular collocation MCTDH (RC-MCTDH) method. It does not require that the potential be a sum of products. RC-MCTDH has the important advantage that it makes it simple to use time-independent collocation points. When using time-independent points, it is necessary to evaluate the potential energy function only once and not repeatedly during an MCTDH calculation. It is inexpensive and straightforward to use RC-MCTDH with combined modes. Using more collocation points than basis functions enables one to reduce errors in energy levels without increasing the size of the single-particle function basis. On the contrary, whenever a discrete variable representation is used, the only way to reduce the quadrature error is to increase the basis size, which then also reduces the basis-set error. We demonstrate that with RC-MCTDH and time-independent points, it is possible to calculate accurate eigenenergies of CH₃ and CH₄.