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231223s2010 xx |||||o 00| ||eng c |
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|a 10.1002/jcc.21547
|2 doi
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|a pubmed24n0669.xml
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|a eng
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|a Berski, Slawomir
|e verfasserin
|4 aut
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|a Ab initio and quantum chemical topology studies on the isomerization of HONO to HNO2. Effect of the basis set in QCT
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|c 2010
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|a Text
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|2 rdacontent
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|a ƒaComputermedien
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|a ƒa Online-Ressource
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|a Date Completed 24.11.2010
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|a Date Revised 21.11.2013
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|a published: Print
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|a Citation Status MEDLINE
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|a 2010 Wiley Periodicals, Inc.
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|a The article focus on the isomerization of nitrous acid HONO to hydrogen nitryl HNO(2). Density functional (B3LYP) and MP2 methods, and a wide variety of basis sets, have been chosen to investigate the mechanism of this reaction. The results clearly show that there are two possible paths: 1) Uncatalysed isomerisation, trans-HONO --> HNO(2), involving 1,2-hydrogen shift and characterized by a large energetic barrier 49.7 divided by 58.9 kcal/mol, 2) Catalysed double hydrogen transfer process, trans-HONO + cis-HONO --> HNO(2) + cis-HONO, which displays a significantly lower energetic barrier in a range of 11.6 divided by 18.9 kcal/mol. Topological analysis of the Electron Localization Function (ELF) shows that the hydrogen transfer for both studied reactions takes place through the formation of a 'dressed' proton along the reaction path. Use of a wide variety of basis sets demonstrates a clear basis set dependence on the ELF topology of HNO(2). Less saturated basis sets yield two lone pair basins, V(1)(N), V(2)(N), whereas more saturated ones (for example aug-cc-pVTZ and aug-cc-pVQZ) do not indicate a lone pair on the nitrogen atom. Topological analysis of the Electron Localizability Indication (ELI-D) at the CASSCF (12,10) confirms these findings, showing the existence of the lone pair basins but with decreasing populations as the basis set becomes more saturated (0.35e for the cc-pVDZ basis set to 0.06e for the aug-cc-pVTZ). This confirms that the choice of basis set not only can influence the value of the electron population at the particular atom, but can also lead to different ELF topology
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|a Journal Article
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|a Nitrous Acid
|2 NLM
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|a T2I5UM75DN
|2 NLM
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|a Latajka, Zdzislaw
|e verfasserin
|4 aut
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|a Gordon, Agnieszka J
|e verfasserin
|4 aut
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| 773 |
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|i Enthalten in
|t Journal of computational chemistry
|d 1984
|g 31(2010), 14 vom: 15. Nov., Seite 2555-67
|w (DE-627)NLM098138448
|x 1096-987X
|7 nnns
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| 773 |
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|g volume:31
|g year:2010
|g number:14
|g day:15
|g month:11
|g pages:2555-67
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|u http://dx.doi.org/10.1002/jcc.21547
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