Alkorta, I., Hill, G. orcid.org/0000-0002-6457-5837 and Legon, A.C. (2020) An ab initio investigation of alkali-metal non-covalent bonds BLiR and BNaR (R = F, H or CH3) formed with simple Lewis bases B : the relative inductive effects of F, H and CH3. Physical Chemistry Chemical Physics, 22 (28). pp. 16421-16430. ISSN 1463-9076
Abstract
The alkali-metal bonds formed by simple molecules LiR and NaR (R = F, H or CH3) with each of the six Lewis bases B = OC, HCN, H2O, H3N, H2S and H3P were investigated by ab initio calculations at the CCSD(T)/AVTZ and CCSD(T)/awCVTZ levels of theory with the aim of characterising this type of non-covalent interaction. In some complexes, two minima were discovered, especially for those involving the NaR. The higher-energy minimum (referred to as Type I) for a given B was found to have geometry that is isomorphous with that of the corresponding hydrogen-bonded analogue BHF. The lower-energy minimum (when two were present) showed evidence of a significant secondary interaction of R with the main electrophilic region of B (Type II complexes). Energies D_e^"CBS" for dissociation of the complexes into separate components were found to be directly proportional to the intermolecular stretching force constant kσ The value of D_e^"CBS" could be partitioned into a nucleophilicity of B and an electrophilicity of LiR or NaR, with the order ELiH ≳ ELiF = ELiCH3 for the LiR and ENaF > ENaH ≈ ENaCH3 for the NaR. For a given B, the order of the electrophilicities is ELiR > ENaR , which presumably reflects the fact that Li+ is smaller than Na+ and can approach the Lewis base more closely. A SAPT analysis revealed that the complexes BLiR and BNaR have larger electrostatic contributions to De than do the hydrogen- and halogen-bonded counterparts BHCl and BClF.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2020 Royal Society of Chemistry. This is an author-produced version of a paper subsequently published in Physical Chemistry Chemical Physics. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 29 Jun 2020 07:20 |
Last Modified: | 03 Nov 2021 17:50 |
Status: | Published |
Publisher: | Royal Society of Chemistry |
Refereed: | Yes |
Identification Number: | 10.1039/D0CP02697B |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:162383 |