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Volumn 22, Issue 12, 2009, Pages 1127-1135

Dispersion interactions in density-functional theory

Author keywords

Density functional theory; Dispersion interactions

Indexed keywords

BOUND SPECIES; COMPUTATIONAL CHEMISTS; DENSITY FUNCTIONALS; DFT METHOD; DISPERSION INTERACTION; FUNCTIONALS; PARAMETERIZED; PHYSICAL ORGANIC CHEMISTRY; PHYSICAL PROCESS;

EID: 72449189196     PISSN: 08943230     EISSN: 10991395     Source Type: Journal    
DOI: 10.1002/poc.1606     Document Type: Article
Times cited : (329)

References (134)
  • 1
    • 0003395607 scopus 로고    scopus 로고
    • See, for example, John Wiley and Sons, Ltd., Chichester, UK
    • These techniques are well-described in a number of modern computational chemistry texts. See, for example, C. J. Cramer, Essentials of Computational Chemistry, John Wiley and Sons, Ltd., Chichester, UK, 2002.
    • (2002) Essentials of Computational Chemistry
    • Cramer, C.J.1
  • 2
    • 72449128072 scopus 로고    scopus 로고
    • note
    • 3.
  • 4
    • 72449143162 scopus 로고    scopus 로고
    • note
    • For example, a coupled-cluster with single and double excitations and perturbative triples, CCSD(T), is considered by many as a 'goldstandard' wavefunction approach. This method scales very poorly with system size (power 7) but has been used to predict, e.g., dispersion binding energies.
  • 5
    • 0003418036 scopus 로고
    • (Ed.: D. R. Yarkony), World Scientific, Singapore
    • A. D. Becke, in: Modern Electronic Structure Theory (Ed.: D. R. Yarkony), World Scientific, Singapore, 1995, pp. 1022-1046.
    • (1995) Modern Electronic Structure Theory , pp. 1022-1046
    • Becke, A.D.1
  • 8
    • 49449097052 scopus 로고    scopus 로고
    • One failing of DFT is the so-called 'static correlation error' which refers to the inability of existing functionals to model chemical systems with high multi-reference character, see A. J. Cohen, P. Mori-Sanchez, W. Yang, Science 2008, 321, 792-794.
    • (2008) Science , vol.321 , pp. 792-794
    • Cohen, A.J.1    Mori-Sanchez, P.2    Yang, W.3
  • 12
    • 0035857407 scopus 로고    scopus 로고
    • The erroneous behavior of B3LYP results in the calculated dissociation energy of the O-H bond in diortho-t-butylphenol to be too low by ca. 5 kcal/mol. This is because the functional predicts too much repulsion between the hydrogen atoms of the OH and t-Bu groups. See J. S. Wright, E. R. Johnson, G. A. DiLabio, J. Am. Chem. Soc. 2001, 123, 1173-1183.
    • (2001) J. Am. Chem. Soc. , vol.123 , pp. 1173-1183
    • Wright, J.S.1    Johnson, E.R.2    DiLabio, G.A.3
  • 25
  • 28
    • 72449190608 scopus 로고    scopus 로고
    • note
    • ij terms. Such explicitly correlated approaches go beyond the HF method and are difficult to solve for anything but the simplest systems. As described briefly in the text, other correlated wavefunction techniques introduce electronic correlation by expanding the HF wavefunction to include excited state electronic configurations.
  • 29
    • 72449190124 scopus 로고    scopus 로고
    • note
    • We note that the parallel orientation is not the minimum energy structure for the benzene dimer. However, the parallel benzene dimer was chosen for comparative purposes for a number of reasons. Firstly, it is large enough to be a physically reasonable model for dispersion interactions that occur in chemistry and biology. Secondly, the high symmetry of this system allows for the calculation of very high-level correlated wavefunction potential energy surface data with which to compare. Finally, the system is a particularly challenging case for DFT methods.
  • 30
    • 72449188198 scopus 로고    scopus 로고
    • note
    • In principle, the exact energy of a chemical system can be computed if an infinitely large (viz. complete) basis set is employed with a wavefunction method that incorporates full electronic correlation. In practice, the complete basis set result is approximated using a scheme in which the energy of a system is extrapolated from energies obtained from finite basis sets.
  • 32
    • 72449125186 scopus 로고    scopus 로고
    • note
    • In most of the DFT approaches, separate functionals are constructed for exchange and correlation.
  • 34
    • 72449142689 scopus 로고    scopus 로고
    • note
    • Some popular GGA functionals include BLYP and PBE. Hybrid GGA functionals, like the very popular B3LYP, include a certain amount of exchange obtained from HF theory. Exchange energies calculated by HF theory are exact. BMK, TPSS, and the M06 family of functionals are examples of meta-GGAs.
  • 45
    • 72449176401 scopus 로고    scopus 로고
    • note
    • 30. Note that most other functionals, including B3LYP, also produce stronger binding with smaller basis sets.
  • 81
    • 72449194269 scopus 로고    scopus 로고
    • E. R. Johnson, F. A. Bulat, H. Hu, W. Yang, submitted
    • E. R. Johnson, F. A. Bulat, H. Hu, W. Yang, submitted.
  • 96
    • 0001333484 scopus 로고    scopus 로고
    • Effective core potentials (ECPs) are commonly used to replace the inner shell electrons of heavy atoms, for example those in the 6th row of the Periodic Table, by simple Gaussian potentials. Doing so reduces the computational cost associated with treating heavy atoms and allows for the inclusion of certain relativistic effects. See, for example, S. A. Wildman, G. A. DiLabio, P. A. Christiansen, J. Chem. Phys. 1997, 107, 9975-9979.
    • (1997) J. Chem. Phys. , vol.107 , pp. 9975-9979
    • Wildman, S.A.1    DiLabio, G.A.2    Christiansen, P.A.3
  • 111
    • 72449122841 scopus 로고    scopus 로고
    • note
    • 97.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.