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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...

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Autores principales: Pawlak, Mariusz, Żuchowski, Piotr S., Moiseyev, Nimrod, Jankowski, Piotr
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
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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.
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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
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