Origin of the Linear Relationship between CH/NH/O—SWNT Reaction Energies and Sidewall Curvature: Armchair Nanotubes.
The origin of the linear relationship between the reaction energy of the CH/NH/O exo and endo additions to armchair (n, n) single-walled carbon nanotubes (SWNTs) and the inverse tube diameter (1/d) measuring sidewall curvature was elucidated using density functional theory and density functional tig...
| Publicado en: | Journal of the American Chemical Society Vol. 128; no. 47; pp. 15117 - 15127 |
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| Autores principales: | , , , |
| Formato: | Artículo |
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American Chemical Society
11/29/2006
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=23404950&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 23404950 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 11/29/2006 vid: 128 iid: 47 pid: 997 pub: American Chemical Society artinfo: ui: 23404950 10.1021/ja061306u ppf: 15117 ppct: 10 formats: tig: atl: Origin of the Linear Relationship between CH/NH/O—SWNT Reaction Energies and Sidewall Curvature: Armchair Nanotubes. aug: au: Guishan Zheng Zhi Wang Irie, Stephan Morokuma, Keiji affil: Cherry L. Emerson Center for Scientific Computation Department of Chemistry, Emory University, Atlanta, Georgia 30322 Department of Chemistry, University of Illinois, Urbana-Champaign, Urbana, IL 61801 Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan su: Nanotubes Chemical reactions Chemical processes Density functionals Functional analysis Potential energy surfaces sug: subj: Nanotubes Chemical reactions Chemical processes Density functionals Functional analysis Potential energy surfaces ab: The origin of the linear relationship between the reaction energy of the CH/NH/O exo and endo additions to armchair (n, n) single-walled carbon nanotubes (SWNTs) and the inverse tube diameter (1/d) measuring sidewall curvature was elucidated using density functional theory and density functional tight binding methods for finite-size SWNT models with n = 3, 4…13. A nearly perfect linear relationship between ΔE and 1/d all through exohedral (positive curvature) and endohedral (negative curvature) additions is due to cancellation between the quadratic contributions of the SWNT deformation energy and the interaction energy (INT) between the deformed SWNT and CH/NH/O adducts. Energy decomposition analysis shows that the quadratic contributions in electrostatic, exchange, and orbital terms mostly cancel each other, making INT weakly quadratic, and that the linear 1/d dependence of INT, and therefore of ΔE, is a reflection of the 1/d dependence of the back-donative orbital interaction of b symmetry from the occupied CH/NH/O pπ orbital to the vacant C=C π* LUMO of the SWNT. We also discuss the origin of the two isomers (open and three-membered ring) of the exohedral addition product and explain the behavior of their associated minima on the C-C potential energy surfaces with changing d. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2006 holdings: @attributes: islocal: N |
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