An Efficient Fragment-Based Approach for Predicting the Ground-State Energies and Structures of Large Molecules.
An efficient fragment-based approach for predicting the ground-state energies and structures of large molecules at the Hartree-Fock (HF) and post-HF levels is described. The physical foundation of this approach is attributed to the "quantum locality" of the electron correlation energy and the HF tot...
| Publicado en: | Journal of the American Chemical Society Vol. 127; no. 19; pp. 7215 - 7227 |
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| Autores principales: | , , |
| Formato: | Artículo |
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American Chemical Society
5/18/2005
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| 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=17105683&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 17105683 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: 5/18/2005 vid: 127 iid: 19 pid: 997 pub: American Chemical Society artinfo: ui: 17105683 10.1021/ja0427247 ppf: 7215 ppct: 12 formats: tig: atl: An Efficient Fragment-Based Approach for Predicting the Ground-State Energies and Structures of Large Molecules. aug: au: Li, Shuhua Li, Wei Fang, Tao affil: Department of Chemistry, Institute of Theoretical and Computational Chemistry, Lab of Mesoscopic Chemistry, Nanjing University, Nanjing, 210093, People's Republic of China. su: Molecules Electron configuration Fullerenes Organic compounds Carbon compounds Electrons sug: subj: Molecules Electron configuration Fullerenes Organic compounds Carbon compounds Electrons ab: An efficient fragment-based approach for predicting the ground-state energies and structures of large molecules at the Hartree-Fock (HF) and post-HF levels is described. The physical foundation of this approach is attributed to the "quantum locality" of the electron correlation energy and the HF total energy, which is revealed by a new energy decomposition analysis of the HF total energy proposed in this work. This approach is based on the molecular fractionation with conjugated caps (MFCC) scheme (Zhang, D. W.; Zhang, J. Z. H. J. Chem. Phys. 2003, 119, 3599), by which a macromolecule is partitioned into various capped fragments and conjugated caps formed by two adjacent caps. We find that the MFCC scheme, if corrected by the interaction between non-neighboring fragments, can be used to predict the total energy of large molecules only from energy calculations on a series of small subsystems. The approach, named as energy-corrected MFCC (EC-MFCC), computationally achieves linear scaling with the molecular size. Our test calculations on a broad range of medium- and large molecules demonstrate that this approach is able to reproduce the conventional HF and second-order Møller-Plesset perturbation theory (MP2) energies within a few millihartree in most cases. With the EC-MFCC optimization algorithm described in this work, we have obtained the optimized structures of long oligomers of trans-polyacetylene and BN nanotubes with up to about 400 atoms, which are beyond the reach of traditional computational methods. In addition, the EC-MFCC approach is also applied to estimate the heats of formation for a series of organic compounds. This approach provides an appealing approach alternative to the traditional additivity rules based on either bond or group contributions for the estimation of thermochemical properties. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2005 holdings: @attributes: islocal: N |
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