Ab initio molecular orbital calculations of solvent clusters of trans-N-methylacetamide: Structure, ring cluster formation and out-of-plane deformation
| dc.contributor.author | Demetropoulos, I. N. | en |
| dc.contributor.author | Gerothanassis, I. P. | en |
| dc.contributor.author | Vakka, C. | en |
| dc.contributor.author | Kakavas, C. | en |
| dc.date.accessioned | 2015-11-24T16:41:45Z | |
| dc.date.available | 2015-11-24T16:41:45Z | |
| dc.identifier.issn | 0956-5000 | - |
| dc.identifier.uri | https://olympias.lib.uoi.gr/jspui/handle/123456789/8466 | |
| dc.rights | Default Licence | - |
| dc.subject | aqueous-solution | en |
| dc.subject | excited-state | en |
| dc.subject | peptide-bond | en |
| dc.subject | amide group | en |
| dc.subject | abinitio | en |
| dc.subject | hydration | en |
| dc.subject | acetonitrile | en |
| dc.subject | biomolecules | en |
| dc.subject | water | en |
| dc.subject | spectroscopy | en |
| dc.title | Ab initio molecular orbital calculations of solvent clusters of trans-N-methylacetamide: Structure, ring cluster formation and out-of-plane deformation | en |
| heal.abstract | The solvation of trans amides has been investigated by the use of full gradient optimization ab initio quantum mechanical calculation techniques. The complexes have been determined at the Hartree-Fock (HF) level with a 4-31G*/4-31G** basis set and at the second-order Moller-Plesset perturbation (MP2) level. Three NMA-water clusters were investigated: trans-NMA with two molecules of water forming a ring cluster at the amide oxygen; trans-NMA with two molecules of water at the amide oxygen forming hydrogen bonds along the direction of the lone-pair electrons; trans-NMA with one molecule of water at the CO group and one at the NH group. In addition, 4-31G* basis set calculations for trans-NMA with two molecules of acetonitrile were performed. The C=O ... H(W) hydrogen bond lengths, electron-density population analysis and molecular-orbital analysis of trans-NMA with two molecules of water at the amide oxygen demonstrate the importance of concurrent water-water and water-(carbonyl) oxygen hydrogen-bond interactions. The complex of trans-NMA with two molecules of water forming a ring cluster at the amide oxygen indicates the formation of a non-planar amide bond and the generation of a chiral centre at the amide nitrogen; this structure has a 5% Boltzmann distribution at room temperature at the MP2 level. Vibrational-frequency analysis shows that its hydrogen-bonded water molecules are vibrationally coupled. Orbital analysis suggests that there is a considerable solute-occupied space reorganization caused by the rearrangement of the water solvent molecules. Comparisons are made with previous theoretical studies of amide-water interactions and experimental spectroscopic, X-ray and neutron-diffraction data on the hydration of amides, peptides and proteins. | en |
| heal.access | campus | - |
| heal.fullTextAvailability | TRUE | - |
| heal.identifier.primary | Doi 10.1039/Ft9969200921 | - |
| heal.identifier.secondary | <Go to ISI>://A1996UD00200005 | - |
| heal.identifier.secondary | http://pubs.rsc.org/en/Content/ArticleLanding/1996/FT/ft9969200921 | - |
| heal.journalName | Journal of the Chemical Society-Faraday Transactions | en |
| heal.journalType | peer reviewed | - |
| heal.language | en | - |
| heal.publicationDate | 1996 | - |
| heal.publisher | Royal Society of Chemistry | en |
| heal.recordProvider | Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας | el |
| heal.type | journalArticle | - |
| heal.type.el | Άρθρο Περιοδικού | el |
| heal.type.en | Journal article | en |
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