The ground-state tunneling splitting of various carboxylic acid dimers
Carboxylic acid dimers in gas phase reveal ground-state tunneling splittings due to a double proton transfer between the two subunits. In this study we apply a recently developed accurate semiclassical method to determine the ground-state tunneling splittings of eight different carboxylic acid deriv...
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craippubl:10.1063/1.1630565 2024-02-11T10:02:52+01:00 The ground-state tunneling splitting of various carboxylic acid dimers Tautermann, Christofer S. Voegele, Andreas F. Liedl, Klaus R. 2003 http://dx.doi.org/10.1063/1.1630565 https://pubs.aip.org/aip/jcp/article-pdf/120/2/631/10855923/631_1_online.pdf en eng AIP Publishing The Journal of Chemical Physics volume 120, issue 2, page 631-637 ISSN 0021-9606 1089-7690 Physical and Theoretical Chemistry General Physics and Astronomy journal-article 2003 craippubl https://doi.org/10.1063/1.1630565 2024-01-26T09:42:35Z Carboxylic acid dimers in gas phase reveal ground-state tunneling splittings due to a double proton transfer between the two subunits. In this study we apply a recently developed accurate semiclassical method to determine the ground-state tunneling splittings of eight different carboxylic acid derivative dimers (formic acid, benzoic acid, carbamic acid, fluoro formic acid, carbonic acid, glyoxylic acid, acrylic acid, and N,N-dimethyl carbamic acid) and their fully deuterated analogs. The calculated splittings range from 5.3e-4 to 0.13 cm−1 (for the deuterated species from 2.8e-7 to 3.3e-4 cm−1), thus indicating a strong substituent dependence of the splitting, which varies by more than two orders of magnitude. One reason for differences in the splittings could be addressed to different barriers heights, which vary from 6.3 to 8.8 kcal/mol, due to different mesomeric stabilization of the various transition states. The calculated splittings were compared to available experimental data and good agreement was found. A correlation could be found between the tunneling splitting and the energy barrier of the double proton transfer, as the splitting increases with increased strength of the hydrogen bonds. From this correlation an empirical formula was derived, which allows the prediction of the ground-state tunneling splitting of carboxylic acid dimers at a very low cost and the tunneling splittings for parahalogen substituted benzoic acid dimers is predicted. Article in Journal/Newspaper Carbonic acid AIP Publishing The Journal of Chemical Physics 120 2 631 637 |
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AIP Publishing |
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English |
topic |
Physical and Theoretical Chemistry General Physics and Astronomy |
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Physical and Theoretical Chemistry General Physics and Astronomy Tautermann, Christofer S. Voegele, Andreas F. Liedl, Klaus R. The ground-state tunneling splitting of various carboxylic acid dimers |
topic_facet |
Physical and Theoretical Chemistry General Physics and Astronomy |
description |
Carboxylic acid dimers in gas phase reveal ground-state tunneling splittings due to a double proton transfer between the two subunits. In this study we apply a recently developed accurate semiclassical method to determine the ground-state tunneling splittings of eight different carboxylic acid derivative dimers (formic acid, benzoic acid, carbamic acid, fluoro formic acid, carbonic acid, glyoxylic acid, acrylic acid, and N,N-dimethyl carbamic acid) and their fully deuterated analogs. The calculated splittings range from 5.3e-4 to 0.13 cm−1 (for the deuterated species from 2.8e-7 to 3.3e-4 cm−1), thus indicating a strong substituent dependence of the splitting, which varies by more than two orders of magnitude. One reason for differences in the splittings could be addressed to different barriers heights, which vary from 6.3 to 8.8 kcal/mol, due to different mesomeric stabilization of the various transition states. The calculated splittings were compared to available experimental data and good agreement was found. A correlation could be found between the tunneling splitting and the energy barrier of the double proton transfer, as the splitting increases with increased strength of the hydrogen bonds. From this correlation an empirical formula was derived, which allows the prediction of the ground-state tunneling splitting of carboxylic acid dimers at a very low cost and the tunneling splittings for parahalogen substituted benzoic acid dimers is predicted. |
format |
Article in Journal/Newspaper |
author |
Tautermann, Christofer S. Voegele, Andreas F. Liedl, Klaus R. |
author_facet |
Tautermann, Christofer S. Voegele, Andreas F. Liedl, Klaus R. |
author_sort |
Tautermann, Christofer S. |
title |
The ground-state tunneling splitting of various carboxylic acid dimers |
title_short |
The ground-state tunneling splitting of various carboxylic acid dimers |
title_full |
The ground-state tunneling splitting of various carboxylic acid dimers |
title_fullStr |
The ground-state tunneling splitting of various carboxylic acid dimers |
title_full_unstemmed |
The ground-state tunneling splitting of various carboxylic acid dimers |
title_sort |
ground-state tunneling splitting of various carboxylic acid dimers |
publisher |
AIP Publishing |
publishDate |
2003 |
url |
http://dx.doi.org/10.1063/1.1630565 https://pubs.aip.org/aip/jcp/article-pdf/120/2/631/10855923/631_1_online.pdf |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
The Journal of Chemical Physics volume 120, issue 2, page 631-637 ISSN 0021-9606 1089-7690 |
op_doi |
https://doi.org/10.1063/1.1630565 |
container_title |
The Journal of Chemical Physics |
container_volume |
120 |
container_issue |
2 |
container_start_page |
631 |
op_container_end_page |
637 |
_version_ |
1790598958770290688 |