Computational study of hydrogen-bonded complexes of HOCO with acids: HOCO⋯HCOOH, HOCO⋯H2SO4, and HOCO⋯H2CO3
Quantum chemistry calculations at the density functional theory (DFT) (B3LYP), MP2, QCISD, QCISD(T), and CCSD(T) levels in conjunction with 6-311++G(2d,2p) and 6-311++G(2df,2p) basis sets have been performed to explore the binding energies of open-shell hydrogen bonded complexes formed between the H...
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craippubl:10.1063/1.4742817 2024-02-11T10:02:52+01:00 Computational study of hydrogen-bonded complexes of HOCO with acids: HOCO⋯HCOOH, HOCO⋯H2SO4, and HOCO⋯H2CO3 Hazra, Montu K. Francisco, Joseph S. Sinha, Amitabha National Science Foundation 2012 http://dx.doi.org/10.1063/1.4742817 https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4742817/14081318/064319_1_online.pdf en eng AIP Publishing The Journal of Chemical Physics volume 137, issue 6 ISSN 0021-9606 1089-7690 Physical and Theoretical Chemistry General Physics and Astronomy journal-article 2012 craippubl https://doi.org/10.1063/1.4742817 2024-01-26T09:42:46Z Quantum chemistry calculations at the density functional theory (DFT) (B3LYP), MP2, QCISD, QCISD(T), and CCSD(T) levels in conjunction with 6-311++G(2d,2p) and 6-311++G(2df,2p) basis sets have been performed to explore the binding energies of open-shell hydrogen bonded complexes formed between the HOCO radical (both cis-HOCO and trans-HOCO) and trans-HCOOH (formic acid), H2SO4 (sulfuric acid), and cis-cis-H2CO3 (carbonic acid). Calculations at the CCSD(T)/6-311++G(2df,2p) level predict that these open-shell complexes have relatively large binding energies ranging between 9.4 to 13.5 kcal/mol and that cis-HOCO (cH) binds more strongly compared to trans-HOCO in these complexes. The zero-point-energy-corrected binding strengths of the cH⋯Acid complexes are comparable to that of the formic acid homodimer complex (∼13–14 kcal/mol). Infrared fundamental frequencies and intensities of the complexes are computed within the harmonic approximation. Infrared spectroscopy is suggested as a potential useful tool for detection of these HOCO⋯Acid complexes in the laboratory as well as in various planetary atmospheres since complex formation is found to induce large frequency shifts and intensity enhancement of the H-bonded OH stretching fundamental relative to that of the corresponding parent monomers. Finally, the ability of an acid molecule such as formic acid to catalyze the inter-conversion between the cis- and trans-HOCO isomers in the gas phase is also discussed. Article in Journal/Newspaper Carbonic acid AIP Publishing Zero Point ENVELOPE(-37.150,-37.150,-54.117,-54.117) The Journal of Chemical Physics 137 6 |
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English |
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Physical and Theoretical Chemistry General Physics and Astronomy |
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Physical and Theoretical Chemistry General Physics and Astronomy Hazra, Montu K. Francisco, Joseph S. Sinha, Amitabha Computational study of hydrogen-bonded complexes of HOCO with acids: HOCO⋯HCOOH, HOCO⋯H2SO4, and HOCO⋯H2CO3 |
topic_facet |
Physical and Theoretical Chemistry General Physics and Astronomy |
description |
Quantum chemistry calculations at the density functional theory (DFT) (B3LYP), MP2, QCISD, QCISD(T), and CCSD(T) levels in conjunction with 6-311++G(2d,2p) and 6-311++G(2df,2p) basis sets have been performed to explore the binding energies of open-shell hydrogen bonded complexes formed between the HOCO radical (both cis-HOCO and trans-HOCO) and trans-HCOOH (formic acid), H2SO4 (sulfuric acid), and cis-cis-H2CO3 (carbonic acid). Calculations at the CCSD(T)/6-311++G(2df,2p) level predict that these open-shell complexes have relatively large binding energies ranging between 9.4 to 13.5 kcal/mol and that cis-HOCO (cH) binds more strongly compared to trans-HOCO in these complexes. The zero-point-energy-corrected binding strengths of the cH⋯Acid complexes are comparable to that of the formic acid homodimer complex (∼13–14 kcal/mol). Infrared fundamental frequencies and intensities of the complexes are computed within the harmonic approximation. Infrared spectroscopy is suggested as a potential useful tool for detection of these HOCO⋯Acid complexes in the laboratory as well as in various planetary atmospheres since complex formation is found to induce large frequency shifts and intensity enhancement of the H-bonded OH stretching fundamental relative to that of the corresponding parent monomers. Finally, the ability of an acid molecule such as formic acid to catalyze the inter-conversion between the cis- and trans-HOCO isomers in the gas phase is also discussed. |
author2 |
National Science Foundation |
format |
Article in Journal/Newspaper |
author |
Hazra, Montu K. Francisco, Joseph S. Sinha, Amitabha |
author_facet |
Hazra, Montu K. Francisco, Joseph S. Sinha, Amitabha |
author_sort |
Hazra, Montu K. |
title |
Computational study of hydrogen-bonded complexes of HOCO with acids: HOCO⋯HCOOH, HOCO⋯H2SO4, and HOCO⋯H2CO3 |
title_short |
Computational study of hydrogen-bonded complexes of HOCO with acids: HOCO⋯HCOOH, HOCO⋯H2SO4, and HOCO⋯H2CO3 |
title_full |
Computational study of hydrogen-bonded complexes of HOCO with acids: HOCO⋯HCOOH, HOCO⋯H2SO4, and HOCO⋯H2CO3 |
title_fullStr |
Computational study of hydrogen-bonded complexes of HOCO with acids: HOCO⋯HCOOH, HOCO⋯H2SO4, and HOCO⋯H2CO3 |
title_full_unstemmed |
Computational study of hydrogen-bonded complexes of HOCO with acids: HOCO⋯HCOOH, HOCO⋯H2SO4, and HOCO⋯H2CO3 |
title_sort |
computational study of hydrogen-bonded complexes of hoco with acids: hoco⋯hcooh, hoco⋯h2so4, and hoco⋯h2co3 |
publisher |
AIP Publishing |
publishDate |
2012 |
url |
http://dx.doi.org/10.1063/1.4742817 https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4742817/14081318/064319_1_online.pdf |
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ENVELOPE(-37.150,-37.150,-54.117,-54.117) |
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Zero Point |
geographic_facet |
Zero Point |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
The Journal of Chemical Physics volume 137, issue 6 ISSN 0021-9606 1089-7690 |
op_doi |
https://doi.org/10.1063/1.4742817 |
container_title |
The Journal of Chemical Physics |
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137 |
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6 |
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1790598961316233216 |