Abstract
A rigorous and efficient approach for the calculation of eigenstates in polyatomic molecular systems with potentials displaying multiple wells is introduced. The scheme is based on the multi-configurational time-dependent Hartree (MCTDH) approach and uses multiple MCTDH wavefunctions with different single-particle function bases to describe the quantum dynamics in the different potential wells. More specifically, an iterative block Lanczos-type diagonalization scheme utilizing state-averaged MCTDH wavefunctions localized in different wells is employed to obtain the energy eigenvalues and eigenstates. The approach does not impose any formal restriction on the symmetry of the potential or the number of wells. A seven-dimensional model system of tetrahedral symmetry, which is inspired by A·CH(4) type complexes and displays four equivalent potential minima, is used to study the numerical performance of the new approach. It is found that the number of configurations in the MCTDH wavefunctions required to obtain converged results is decreased by roughly one order of magnitude compared to standard MCTDH calculations employing a block-relaxation scheme.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.