How to Model Inter- and Intramolecular Hydrogen Bond Strengths with Quantum Chemistry
This article presents the computation of both inter- and intramolecular hydrogen bond strengths from first-principles. Quantum chemical calculations conducted at the dispersion-corrected density functional theory level including free energy and solvation contributions are conducted for (i) one-to-on...
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Published in | Journal of chemical information and modeling Vol. 59; no. 9; pp. 3735 - 3743 |
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Main Author | |
Format | Journal Article |
Language | English |
Published |
United States
American Chemical Society
23.09.2019
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Subjects | |
Online Access | Get full text |
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Summary: | This article presents the computation of both inter- and intramolecular hydrogen bond strengths from first-principles. Quantum chemical calculations conducted at the dispersion-corrected density functional theory level including free energy and solvation contributions are conducted for (i) one-to-one hydrogen-bonded complexes of alcohols to N-methyl pyrrolidinone measured by an infrared spectroscopy method and (ii) a set of experimental intramolecular hydrogen bond-forming phenol and pyrrole compounds, with intramolecular hydrogen bond strengths derived from a nuclear magnetic resonance method. The computed complexation free energies in solution show a correlation to experiment of R 2 = 0.74 with a root mean square error of 4.85 kJ mol–1. The intramolecular hydrogen bonding free energies in solution show a correlation of R 2 = 0.79 with a root mean square error of 5.51 kJ mol–1. The results of this study can be used as a guide on how to build reliable quantum chemical databases for computed hydrogen bonding strengths. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1549-9596 1549-960X |
DOI: | 10.1021/acs.jcim.9b00132 |