Please use this identifier to cite or link to this item: http://localhost:8080/xmlui/handle/123456789/1468
Full metadata record
DC FieldValueLanguage
dc.contributor.authorRemya, K-
dc.contributor.authorSuresh, C H-
dc.date.accessioned2014-05-27T09:01:58Z-
dc.date.available2014-05-27T09:01:58Z-
dc.date.issued2014-
dc.identifier.citationJournal of Computational Chemistry 35(12):910–922;5 May 2014en_US
dc.identifier.issn0192-8651-
dc.identifier.urihttp://ir.niist.res.in:8080/jspui/handle/123456789/1468-
dc.description.abstractCooperativity in intermolecular interactions and cluster growth patterns of acetonitrile has been studied using M06L density functional theory. Cyclic, ladder-type, stacked, cross-stacked, and mixed patterns are studied. Total interaction energy (E-int) and interaction energy per monomer (E-m) show maximum stability and cooperativity in stacked clusters followed by cross-stacked ones. As cluster size increased, magnitude of E-m showed significant increase. Compared to E-m of dimer (-2.97 kcal/mol), the increase is 2.6-fold for 27mer. Higher stabilization in larger clusters is attributed to strong cooperativity in intermolecular CHN and dipolar interactions. Enhanced cooperativity in stacked structures is supported by atoms-in-molecule electron density () data. Sum of at intermolecular bond critical points is the highest for stacked clusters. Further, area of negative-valued molecular electrostatic potential is linearly related with E-int and showed the lowest value in stacked followed by cross-stacked clusters, indicating maximum utilization of lone pair density and maximum cooperativity in such growth patterns. A red shift in the average CN stretching frequencies with increase in the number of monomers and its direct correlation with E-int in stacked clusters also supported their stability. Further, two known crystal patterns of acetonitrile (alpha and beta) with 16 monomers are optimized and compared with the most stable hexadecamer pattern and are found to show lower values for E-int and E-m compared to the latter. Based on this result, we predict the existence of a third crystal pattern for acetonitrile which will be more ordered and more stable than alpha and beta forms.en_US
dc.language.isoenen_US
dc.publisherWiley Periodicalsen_US
dc.subjectHydrogen bondsen_US
dc.subjectDipoleen_US
dc.subjectCluster formationen_US
dc.subjectAcetonitrileen_US
dc.titleCooperativity and cluster growth patterns in acetonitrile: A DFT studyen_US
dc.typeArticleen_US
Appears in Collections:2014

Files in This Item:
File Description SizeFormat 
2014-36.pdf
  Restricted Access
1.61 MBAdobe PDFView/Open Request a copy


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.