Cooperative effects in two-dimensional ring-like networks of three-center hydrogen bonding interactions
Cooperative effects in two-dimensional cyclic networks containing intermolecular three-centered hydrogen bonding interactions of the type H1…A…H2 are investigated by means of ab intio molecular orbital and density functional theory calculations. Ring-like clusters consisting of three and up to nine...
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craippubl:10.1063/1.1895713 2024-02-11T10:02:52+01:00 Cooperative effects in two-dimensional ring-like networks of three-center hydrogen bonding interactions Parra, Rubén D. Bulusu, Satya Zeng, X. C. 2005 http://dx.doi.org/10.1063/1.1895713 https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.1895713/13374050/184325_1_online.pdf en eng AIP Publishing The Journal of Chemical Physics volume 122, issue 18 ISSN 0021-9606 1089-7690 Physical and Theoretical Chemistry General Physics and Astronomy journal-article 2005 craippubl https://doi.org/10.1063/1.1895713 2024-01-26T09:48:46Z Cooperative effects in two-dimensional cyclic networks containing intermolecular three-centered hydrogen bonding interactions of the type H1…A…H2 are investigated by means of ab intio molecular orbital and density functional theory calculations. Ring-like clusters consisting of three and up to nine monomers of the cis–cis isomer of carbonic acid H2CO3 are used as basic models, where each unit acts simultaneously as a double hydrogen-bond donor and double hydrogen-bond acceptor. Cooperative effects based on binding energies are evident for (H2CO3)n, where n goes from 2 to 9. Thus, the ZPVE-corrected dissociation energy per bifurcated hydrogen bond increases from 11.52kcal∕mol in the dimer to 20.42kcal∕mol in the nonamer, i.e., a 77% cooperative enhancement. Cooperative effects are also manifested in such indicators as geometries, and vibrational frequencies and intensities. The natural bond orbital analysis method is used to rationalize the results in terms of the substantial charge delocalization taking place in the cyclic clusters. Cooperativity seems close to reaching an asymptotic limit in the largest ring considered, n=9. Article in Journal/Newspaper Carbonic acid AIP Publishing The Journal of Chemical Physics 122 18 |
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Open Polar |
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AIP Publishing |
op_collection_id |
craippubl |
language |
English |
topic |
Physical and Theoretical Chemistry General Physics and Astronomy |
spellingShingle |
Physical and Theoretical Chemistry General Physics and Astronomy Parra, Rubén D. Bulusu, Satya Zeng, X. C. Cooperative effects in two-dimensional ring-like networks of three-center hydrogen bonding interactions |
topic_facet |
Physical and Theoretical Chemistry General Physics and Astronomy |
description |
Cooperative effects in two-dimensional cyclic networks containing intermolecular three-centered hydrogen bonding interactions of the type H1…A…H2 are investigated by means of ab intio molecular orbital and density functional theory calculations. Ring-like clusters consisting of three and up to nine monomers of the cis–cis isomer of carbonic acid H2CO3 are used as basic models, where each unit acts simultaneously as a double hydrogen-bond donor and double hydrogen-bond acceptor. Cooperative effects based on binding energies are evident for (H2CO3)n, where n goes from 2 to 9. Thus, the ZPVE-corrected dissociation energy per bifurcated hydrogen bond increases from 11.52kcal∕mol in the dimer to 20.42kcal∕mol in the nonamer, i.e., a 77% cooperative enhancement. Cooperative effects are also manifested in such indicators as geometries, and vibrational frequencies and intensities. The natural bond orbital analysis method is used to rationalize the results in terms of the substantial charge delocalization taking place in the cyclic clusters. Cooperativity seems close to reaching an asymptotic limit in the largest ring considered, n=9. |
format |
Article in Journal/Newspaper |
author |
Parra, Rubén D. Bulusu, Satya Zeng, X. C. |
author_facet |
Parra, Rubén D. Bulusu, Satya Zeng, X. C. |
author_sort |
Parra, Rubén D. |
title |
Cooperative effects in two-dimensional ring-like networks of three-center hydrogen bonding interactions |
title_short |
Cooperative effects in two-dimensional ring-like networks of three-center hydrogen bonding interactions |
title_full |
Cooperative effects in two-dimensional ring-like networks of three-center hydrogen bonding interactions |
title_fullStr |
Cooperative effects in two-dimensional ring-like networks of three-center hydrogen bonding interactions |
title_full_unstemmed |
Cooperative effects in two-dimensional ring-like networks of three-center hydrogen bonding interactions |
title_sort |
cooperative effects in two-dimensional ring-like networks of three-center hydrogen bonding interactions |
publisher |
AIP Publishing |
publishDate |
2005 |
url |
http://dx.doi.org/10.1063/1.1895713 https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.1895713/13374050/184325_1_online.pdf |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
The Journal of Chemical Physics volume 122, issue 18 ISSN 0021-9606 1089-7690 |
op_doi |
https://doi.org/10.1063/1.1895713 |
container_title |
The Journal of Chemical Physics |
container_volume |
122 |
container_issue |
18 |
_version_ |
1790598952333082624 |