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231225s2018 xx |||||o 00| ||eng c |
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|a 10.1002/jcc.25082
|2 doi
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|a pubmed24n0925.xml
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|e rakwb
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|a eng
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|a Bijina, Padinjare Veetil
|e verfasserin
|4 aut
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|a Electrostatics for probing lone pairs and their interactions
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|c 2018
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|a Text
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|a ƒaComputermedien
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|a ƒa Online-Ressource
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|a Date Completed 09.09.2019
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|a Date Revised 09.09.2019
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|a published: Print-Electronic
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|a Citation Status PubMed-not-MEDLINE
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|a © 2017 Wiley Periodicals, Inc.
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|a The value of the molecular electrostatic potential minimum (Vmin ) and its topographical features (position, as well as the eigenvalues and eigenvectors of the corresponding Hessian matrix) are recently proposed as the criteria for characterizing a lone pair (Kumar A. et al., J. Phys. Chem. 2014, A118, 526). This electrostatic characterization of lone pairs is examined for a large number of small molecules employing MP4/6-311++G(d,p)//MP2/6-311++G(d,p) theory. The eigenvector of the Hessian matrix corresponding to its largest eigenvalue (λmax ), is found to be directed toward the lone pair-bearing-atom, with λmax showing a strong linear correlation with Vmin . Large magnitudes of Vmin and λmax indicate a charge-dense lone pair. The topographical features of Vmin are seen to provide insights into the interactive behavior of the molecules with model electrophiles, viz. HF, CO2 , and Li+ . In all the complexes of HF and majority of the other complexes, the interaction energy (Eint ) correlates well with the respective Vmin, value, but for some deviations occurring due to other competing secondary interactions. The electrostatic interactions are found to be highly directional in nature as the orientation of interacting atom correlates strongly to the position of lone pair. In summary, the present study on a large number of test molecules shows that electrostatics is able to probe lone pairs in molecules and offers a simple interpretation of chemical reactivity. © 2017 Wiley Periodicals, Inc
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|a Journal Article
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|a Research Support, Non-U.S. Gov't
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|a chemical reactivity
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|a critical points
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|a lone pairs
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|a molecular electrostatic potential
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|a Suresh, Cherumuttathu H
|e verfasserin
|4 aut
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1 |
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|a Gadre, Shridhar R
|e verfasserin
|4 aut
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|i Enthalten in
|t Journal of computational chemistry
|d 1984
|g 39(2018), 9 vom: 05. Apr., Seite 488-499
|w (DE-627)NLM098138448
|x 1096-987X
|7 nnns
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| 773 |
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|g volume:39
|g year:2018
|g number:9
|g day:05
|g month:04
|g pages:488-499
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|u http://dx.doi.org/10.1002/jcc.25082
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