Dihydrogen Bonding—Seen through the Eyes of Vibrational Spectroscopy
In this work, we analyzed five groups of different dihydrogen bonding interactions and hydrogen clusters with an H<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msubsup><mrow></mrow><mn>3<...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-12-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/1/263 |
| _version_ | 1797431431431979008 |
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| author | Marek Freindorf Margaret McCutcheon Nassim Beiranvand Elfi Kraka |
| author_facet | Marek Freindorf Margaret McCutcheon Nassim Beiranvand Elfi Kraka |
| author_sort | Marek Freindorf |
| collection | DOAJ |
| description | In this work, we analyzed five groups of different dihydrogen bonding interactions and hydrogen clusters with an H<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msubsup><mrow></mrow><mn>3</mn><mo>+</mo></msubsup></semantics></math></inline-formula> kernel utilizing the local vibrational mode theory, developed by our group, complemented with the Quantum Theory of Atoms–in–Molecules analysis to assess the strength and nature of the dihydrogen bonds in these systems. We could show that the intrinsic strength of the dihydrogen bonds investigated is primarily related to the protonic bond as opposed to the hydridic bond; thus, this should be the region of focus when designing dihydrogen bonded complexes with a particular strength. We could also show that the popular discussion of the blue/red shifts of dihydrogen bonding based on the normal mode frequencies is hampered from mode–mode coupling and that a blue/red shift discussion based on local mode frequencies is more meaningful. Based on the bond analysis of the H<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msubsup><mrow></mrow><mn>3</mn><mo>+</mo></msubsup></semantics></math></inline-formula>(H<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>)<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mi>n</mi></msub></semantics></math></inline-formula> systems, we conclude that the bond strength in these crystal–like structures makes them interesting for potential hydrogen storage applications. |
| first_indexed | 2024-03-09T09:44:55Z |
| format | Article |
| id | doaj.art-97babd6952b24d0ea88a73bc09cd0503 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T09:44:55Z |
| publishDate | 2022-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-97babd6952b24d0ea88a73bc09cd05032023-12-02T00:41:47ZengMDPI AGMolecules1420-30492022-12-0128126310.3390/molecules28010263Dihydrogen Bonding—Seen through the Eyes of Vibrational SpectroscopyMarek Freindorf0Margaret McCutcheon1Nassim Beiranvand2Elfi Kraka3Computational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University, 3215 Daniel Ave, Dallas, TX 75275-0314, USAComputational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University, 3215 Daniel Ave, Dallas, TX 75275-0314, USAComputational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University, 3215 Daniel Ave, Dallas, TX 75275-0314, USAComputational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University, 3215 Daniel Ave, Dallas, TX 75275-0314, USAIn this work, we analyzed five groups of different dihydrogen bonding interactions and hydrogen clusters with an H<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msubsup><mrow></mrow><mn>3</mn><mo>+</mo></msubsup></semantics></math></inline-formula> kernel utilizing the local vibrational mode theory, developed by our group, complemented with the Quantum Theory of Atoms–in–Molecules analysis to assess the strength and nature of the dihydrogen bonds in these systems. We could show that the intrinsic strength of the dihydrogen bonds investigated is primarily related to the protonic bond as opposed to the hydridic bond; thus, this should be the region of focus when designing dihydrogen bonded complexes with a particular strength. We could also show that the popular discussion of the blue/red shifts of dihydrogen bonding based on the normal mode frequencies is hampered from mode–mode coupling and that a blue/red shift discussion based on local mode frequencies is more meaningful. Based on the bond analysis of the H<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msubsup><mrow></mrow><mn>3</mn><mo>+</mo></msubsup></semantics></math></inline-formula>(H<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>)<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mi>n</mi></msub></semantics></math></inline-formula> systems, we conclude that the bond strength in these crystal–like structures makes them interesting for potential hydrogen storage applications.https://www.mdpi.com/1420-3049/28/1/263dihydrogen bondinglocal vibrational mode analysisblue/red shiftshydride complexeshydrogen storage |
| spellingShingle | Marek Freindorf Margaret McCutcheon Nassim Beiranvand Elfi Kraka Dihydrogen Bonding—Seen through the Eyes of Vibrational Spectroscopy Molecules dihydrogen bonding local vibrational mode analysis blue/red shifts hydride complexes hydrogen storage |
| title | Dihydrogen Bonding—Seen through the Eyes of Vibrational Spectroscopy |
| title_full | Dihydrogen Bonding—Seen through the Eyes of Vibrational Spectroscopy |
| title_fullStr | Dihydrogen Bonding—Seen through the Eyes of Vibrational Spectroscopy |
| title_full_unstemmed | Dihydrogen Bonding—Seen through the Eyes of Vibrational Spectroscopy |
| title_short | Dihydrogen Bonding—Seen through the Eyes of Vibrational Spectroscopy |
| title_sort | dihydrogen bonding seen through the eyes of vibrational spectroscopy |
| topic | dihydrogen bonding local vibrational mode analysis blue/red shifts hydride complexes hydrogen storage |
| url | https://www.mdpi.com/1420-3049/28/1/263 |
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