Cargando…
Evidence of Nonrigidity Effects in the Description of Low-Energy Anisotropic Molecular Collisions of Hydrogen Molecules with Excited Metastable Helium Atoms
[Image: see text] Cold collisions serve as a sensitive probe of the interaction potential. In the recent study of Klein et al. (Nature Phys.2017, 13, 35–38), the one-parameter scaling of the interaction potential was necessary to obtain agreement between theoretical and observed patterns of the orbi...
Autores principales: | , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2020
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7497643/ https://www.ncbi.nlm.nih.gov/pubmed/32150402 http://dx.doi.org/10.1021/acs.jctc.0c00183 |
_version_ | 1783583358896308224 |
---|---|
author | Pawlak, Mariusz Żuchowski, Piotr S. Moiseyev, Nimrod Jankowski, Piotr |
author_facet | Pawlak, Mariusz Żuchowski, Piotr S. Moiseyev, Nimrod Jankowski, Piotr |
author_sort | Pawlak, Mariusz |
collection | PubMed |
description | [Image: see text] Cold collisions serve as a sensitive probe of the interaction potential. In the recent study of Klein et al. (Nature Phys.2017, 13, 35–38), the one-parameter scaling of the interaction potential was necessary to obtain agreement between theoretical and observed patterns of the orbiting resonances for excited metastable helium atoms colliding with hydrogen molecules. Here, we show that the effect of nonrigidity of the H(2) molecule on the resonant structure, absent in the previous study, is critical to predict the correct positions of the resonances in that case. We have complemented the theoretical description of the interaction potential and revised reaction rate coefficients by proper inclusion of the flexibility of the molecule. The calculated reaction rate coefficients are in remarkable agreement with the experimental data without empirical adjustment of the interaction potential. We have shown that even state-of-the-art calculations of the interaction energy cannot ensure agreement with the experiment if such an important physical effect as flexibility of the interacting molecule is neglected. Our findings about the significance of the nonrigidity effects can be especially crucial in cold chemistry, where the quantum nature of molecules is pronounced. |
format | Online Article Text |
id | pubmed-7497643 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | American
Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-74976432020-09-18 Evidence of Nonrigidity Effects in the Description of Low-Energy Anisotropic Molecular Collisions of Hydrogen Molecules with Excited Metastable Helium Atoms Pawlak, Mariusz Żuchowski, Piotr S. Moiseyev, Nimrod Jankowski, Piotr J Chem Theory Comput [Image: see text] Cold collisions serve as a sensitive probe of the interaction potential. In the recent study of Klein et al. (Nature Phys.2017, 13, 35–38), the one-parameter scaling of the interaction potential was necessary to obtain agreement between theoretical and observed patterns of the orbiting resonances for excited metastable helium atoms colliding with hydrogen molecules. Here, we show that the effect of nonrigidity of the H(2) molecule on the resonant structure, absent in the previous study, is critical to predict the correct positions of the resonances in that case. We have complemented the theoretical description of the interaction potential and revised reaction rate coefficients by proper inclusion of the flexibility of the molecule. The calculated reaction rate coefficients are in remarkable agreement with the experimental data without empirical adjustment of the interaction potential. We have shown that even state-of-the-art calculations of the interaction energy cannot ensure agreement with the experiment if such an important physical effect as flexibility of the interacting molecule is neglected. Our findings about the significance of the nonrigidity effects can be especially crucial in cold chemistry, where the quantum nature of molecules is pronounced. American Chemical Society 2020-03-09 2020-04-14 /pmc/articles/PMC7497643/ /pubmed/32150402 http://dx.doi.org/10.1021/acs.jctc.0c00183 Text en Copyright © 2020 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. |
spellingShingle | Pawlak, Mariusz Żuchowski, Piotr S. Moiseyev, Nimrod Jankowski, Piotr Evidence of Nonrigidity Effects in the Description of Low-Energy Anisotropic Molecular Collisions of Hydrogen Molecules with Excited Metastable Helium Atoms |
title | Evidence of Nonrigidity Effects in the Description
of Low-Energy Anisotropic Molecular Collisions of Hydrogen Molecules
with Excited Metastable Helium Atoms |
title_full | Evidence of Nonrigidity Effects in the Description
of Low-Energy Anisotropic Molecular Collisions of Hydrogen Molecules
with Excited Metastable Helium Atoms |
title_fullStr | Evidence of Nonrigidity Effects in the Description
of Low-Energy Anisotropic Molecular Collisions of Hydrogen Molecules
with Excited Metastable Helium Atoms |
title_full_unstemmed | Evidence of Nonrigidity Effects in the Description
of Low-Energy Anisotropic Molecular Collisions of Hydrogen Molecules
with Excited Metastable Helium Atoms |
title_short | Evidence of Nonrigidity Effects in the Description
of Low-Energy Anisotropic Molecular Collisions of Hydrogen Molecules
with Excited Metastable Helium Atoms |
title_sort | evidence of nonrigidity effects in the description
of low-energy anisotropic molecular collisions of hydrogen molecules
with excited metastable helium atoms |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7497643/ https://www.ncbi.nlm.nih.gov/pubmed/32150402 http://dx.doi.org/10.1021/acs.jctc.0c00183 |
work_keys_str_mv | AT pawlakmariusz evidenceofnonrigidityeffectsinthedescriptionoflowenergyanisotropicmolecularcollisionsofhydrogenmoleculeswithexcitedmetastableheliumatoms AT zuchowskipiotrs evidenceofnonrigidityeffectsinthedescriptionoflowenergyanisotropicmolecularcollisionsofhydrogenmoleculeswithexcitedmetastableheliumatoms AT moiseyevnimrod evidenceofnonrigidityeffectsinthedescriptionoflowenergyanisotropicmolecularcollisionsofhydrogenmoleculeswithexcitedmetastableheliumatoms AT jankowskipiotr evidenceofnonrigidityeffectsinthedescriptionoflowenergyanisotropicmolecularcollisionsofhydrogenmoleculeswithexcitedmetastableheliumatoms |