Degeneracy in discrete variable representations: General considerations and application to the multiconfigurational time-dependent Hartree approach
van Harrevelt, R.
Manthe, Uwe
Problems appear in discrete variable representations (DVRs) based on general basis sets when the coordinate matrix has degenerate eigenvalues. Then the DVR is not uniquely defined. This paper shows that this problem can be caused by symmetry. Taking the symmetry into account when constructing the DVR solves the problem. The symmetry effect can be particularly important for the time-dependent DVR used in multiconfigurational time-dependent Hartree calculations employing the correlation DVR (CDVR) approach. Problems reported previously for the initial-state selected treatment of the H+H-2 reaction can be attributed to this symmetry effect. They can be solved by using a symmetry-adapted approach to construct the time-dependent DVR. Thus, the present paper shows that the CDVR scheme can be employed also in initial-state selected scattering calculations if the symmetry of the system is properly taken into account in the construction of the time-dependent DVR. (C) 2004 American Institute of Physics.
2004
info:eu-repo/semantics/article
doc-type:article
text
https://pub.uni-bielefeld.de/record/1897106
van Harrevelt R, Manthe U. Degeneracy in discrete variable representations: General considerations and application to the multiconfigurational time-dependent Hartree approach. <em>Journal of Chemical Physics</em>. 2004;121(12):5623-5628.
eng
info:eu-repo/semantics/altIdentifier/doi/10.1063/1.1782811
info:eu-repo/semantics/altIdentifier/issn/0021-9606
info:eu-repo/semantics/altIdentifier/wos/000223872000008
info:eu-repo/semantics/altIdentifier/pmid/15366985
info:eu-repo/semantics/closedAccess