# Degeneracy in discrete variable representations: General considerations and application to the multiconfigurational time-dependent Hartree approach

van Harrevelt R, Manthe U (2004)

Journal of Chemical Physics 121(12): 5623-5628.

*Journal Article*|

*Published*|

*English*

No fulltext has been uploaded

Author

van Harrevelt, R.
;
Manthe, Uwe

^{UniBi}Abstract

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.

Publishing Year

ISSN

PUB-ID

### Cite this

van Harrevelt R, Manthe U. Degeneracy in discrete variable representations: General considerations and application to the multiconfigurational time-dependent Hartree approach.

*Journal of Chemical Physics*. 2004;121(12):5623-5628.van Harrevelt, R., & Manthe, U. (2004). Degeneracy in discrete variable representations: General considerations and application to the multiconfigurational time-dependent Hartree approach.

*Journal of Chemical Physics*,*121*(12), 5623-5628.van Harrevelt, R., and Manthe, U. (2004). Degeneracy in discrete variable representations: General considerations and application to the multiconfigurational time-dependent Hartree approach.

*Journal of Chemical Physics*121, 5623-5628.van Harrevelt, R., & Manthe, U., 2004. Degeneracy in discrete variable representations: General considerations and application to the multiconfigurational time-dependent Hartree approach.

*Journal of Chemical Physics*, 121(12), p 5623-5628.R. van Harrevelt and U. Manthe, “Degeneracy in discrete variable representations: General considerations and application to the multiconfigurational time-dependent Hartree approach”,

*Journal of Chemical Physics*, vol. 121, 2004, pp. 5623-5628.van Harrevelt, R., Manthe, U.: Degeneracy in discrete variable representations: General considerations and application to the multiconfigurational time-dependent Hartree approach. Journal of Chemical Physics. 121, 5623-5628 (2004).

van Harrevelt, R., and Manthe, Uwe. “Degeneracy in discrete variable representations: General considerations and application to the multiconfigurational time-dependent Hartree approach”.

*Journal of Chemical Physics*121.12 (2004): 5623-5628.
This data publication is cited in the following publications:

This publication cites the following data publications:

### 3 Citations in Europe PMC

Data provided by Europe PubMed Central.

A multilayer multiconfigurational time-dependent Hartree approach for quantum dynamics on general potential energy surfaces.

Manthe U.,

PMID: 18447430

Manthe U.,

*J Chem Phys*128(16), 2008PMID: 18447430

Calculating initial-state-selected reaction probabilities from thermal flux eigenstates: a transition-state-based approach.

Huarte-Larranaga F, Manthe U.,

PMID: 16351247

Huarte-Larranaga F, Manthe U.,

*J Chem Phys*123(20), 2005PMID: 16351247

Multidimensional time-dependent discrete variable representations in multiconfiguration Hartree calculations.

van Harrevelt R, Manthe U.,

PMID: 16122299

van Harrevelt R, Manthe U.,

*J Chem Phys*123(6), 2005PMID: 16122299

### Export

0 Marked Publications### Web of Science

View record in Web of Science®### Sources

PMID: 15366985

PubMed | Europe PMC