Send to

Choose Destination
See comment in PubMed Commons below
J Phys Chem A. 2013 Aug 15;117(32):7246-55. doi: 10.1021/jp401129t. Epub 2013 Apr 26.

Iterative diagonalization in the multiconfigurational time-dependent Hartree approach: ro-vibrational eigenstates.

Author information

Theoretische Chemie, Fakultät für Chemie, Universität Bielefeld, Universitätsstrasse. 25, D-33615 Bielefeld, Germany.


A scheme to efficiently calculate ro-vibrational (J > 0) eigenstates within the framework of the multiconfigurational time-dependent Hartree (MCTDH) approach is introduced. It employs a basis of MCTDH wave packets which is generated in the calculation of vibrational (J = 0) eigenstates via existing MCTDH-based iterative diagonalization approaches. The subsequent ro-vibrational calculations for total angular momenta J > 0 use direct products of these wave packets and the Wigner rotation matrices. In this ro-vibrational basis, the Hamiltonian matrix can be computed and diagonalized with minor numerical effort for any value of J. Accurate ro-vibrational states are obtained if the number of iterations in the J = 0 calculations and the basis set sizes in the MCTDH wave function representation are converged. Test calculations studying CH2D show that ro-vibrational eigenstates for moderately large J can be converged within wavenumber accuracy with the same MCTDH basis sets and only slightly increased iteration counts compared to purely vibrational (J = 0) calculations. If large J's are considered or very high accuracies are required, the number of iterations required to obtain convergence increases significantly. Comparing the theoretical results with experimental data for the out-of-plane bend, symmetric stretch, and antisymmetric stretch fundamentals, the accuracy of the ab initio potential energy surface employed is investigated.

PubMed Commons home

PubMed Commons

How to join PubMed Commons

    Supplemental Content

    Full text links

    Icon for American Chemical Society
    Loading ...
    Support Center