Dispersion Interactions in Density‐Functional Theory

Density-functional theory (DFT) allows for the calculation of many chemical properties with relative ease, thus making it extremely useful for the physical organic chemistry community to understand and focus on various experiments. However, density-functional techniques have their limitations, including the ability to satisfactorily describe dispersion interactions. Given the ubiquitous nature of dispersion in chemical and biological systems, this is not a trivial matter. Recent advances in the development of DFT methods can treat dispersion. These include dispersion-corrected DFT (using explicit, attractive dispersion terms), parameterized functionals, and dispersion-correcting potentials, all of which can dramatically improve performance for dispersion-bound species. In this perspective, we highlight the achievements made in modeling dispersion using DFT. We hope that this will provide valuable insight to both computational chemists and experimentalists, who aim to study physical processes driven by dispersion interactions. Copyright © 2009 John Wiley & Sons, Ltd.

[1]  C David Sherrill,et al.  Oscillations in meta-generalized-gradient approximation potential energy surfaces for dispersion-bound complexes. , 2009, The Journal of chemical physics.

[2]  P. Ayers.  A perspective on the link between the exchange(-correlation) hole and dispersion forces , 2009 .

[3]  G. DiLabio,et al.  Binding in thiophene and benzothiophene dimers investigated by density functional theory with dispersion-correcting potentials. , 2009, Journal of Physical Chemistry A.

[4]  D. Cremer,et al.  An efficient algorithm for the density-functional theory treatment of dispersion interactions. , 2009, The Journal of chemical physics.

[5]  A. Becke,et al.  Van der Waals Interactions in Density-Functional Theory: Rare-Gas Diatomics. , 2009, Journal of chemical theory and computation.

[6]  D. Langreth,et al.  Van Der Waals Interactions In Density Functional Theory , 2007 .

[7]  G. DiLabio,et al.  Theoretical Study of Dispersion Binding of Hydrocarbon Molecules to Hydrogen-Terminated Silicon(100)-2×1 , 2009 .

[8]  A. Hesselmann.  Derivation of the dispersion energy as an explicit density- and exchange-hole functional. , 2009, The Journal of chemical physics.

[9]  U. Rothlisberger,et al.  Accurate DFT Descriptions for Weak Interactions of Molecules Containing Sulfur. , 2009, Journal of chemical theory and computation.

[10]  Y. Chabal,et al.  Theoretical and experimental analysis of H2 binding in a prototypical metal-organic framework material , 2008, 0812.2700.

[11]  M. Head‐Gordon,et al.  Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections. , 2008, Physical chemistry chemical physics : PCCP.

[12]  P. Schleyer,et al.  Empirical corrections to density functional theory highlight the importance of nonbonded intramolecular interactions in alkanes. , 2008, Journal of Physical Chemistry A.

[13]  P. Hobza,et al.  Benzene Dimer: Dynamic Structure and Thermodynamics Derived from On-the-Fly ab initio DFT-D Molecular Dynamic Simulations. , 2008, Journal of chemical theory and computation.

[14]  G. DiLabio,et al.  Interactions in large, polyaromatic hydrocarbon dimers: application of density functional theory with dispersion corrections. , 2008, The journal of physical chemistry. A.

[15]  Bernd Engels,et al.  Exciton trapping in pi-conjugated materials: a quantum-chemistry-based protocol applied to perylene bisimide dye aggregates. , 2008, Journal of the American Chemical Society.

[16]  Weitao Yang,et al.  Insights into Current Limitations of Density Functional Theory , 2008, Science.

[17]  T. Van Voorhis,et al.  Self-consistent implementation of a nonlocal van der Waals density functional with a Gaussian basis set. , 2008, The Journal of chemical physics.

[18]  D. Langreth,et al.  An application of the van der Waals density functional: Hydrogen bonding and stacking interactions between nucleobases. , 2008, The Journal of chemical physics.

[19]  U. Rothlisberger,et al.  Describing weak interactions of biomolecules with dispersion-corrected density functional theory. , 2008, Physical chemistry chemical physics : PCCP.

[20]  S. Tsuzuki,et al.  CH/pi interactions in methane clusters with polycyclic aromatic hydrocarbons. , 2008, Physical chemistry chemical physics : PCCP.

[21]  Pavel Hobza,et al.  Benchmark database on isolated small peptides containing an aromatic side chain: comparison between wave function and density functional theory methods and empirical force field. , 2008, Physical chemistry chemical physics : PCCP.

[22]  S. Wetmore,et al.  Computational comparison of the stacking interactions between the aromatic amino acids and the natural or (cationic) methylated nucleobases. , 2008, Physical chemistry chemical physics : PCCP.

[23]  U. Rothlisberger,et al.  Atom-Centered Potentials to Describe Dispersion Forces in Density Functional Theory , 2008 .

[24]  G. DiLabio,et al.  Accurate treatment of van der Waals interactions using standard density functional theory methods with effective core-type potentials: Application to carbon-containing dimers , 2008 .

[25]  A. Becke,et al.  A unified density-functional treatment of dynamical, nondynamical, and dispersion correlations. II. Thermochemical and kinetic benchmarks. , 2008, The Journal of chemical physics.

[26]  Kevin E. Riley,et al.  A DFT-D investigation of the mechanisms for activation of the wild-type and S810L mutated mineralocorticoid receptor by steroid hormones. , 2008, Journal of Physical Chemistry B.

[27]  D. Langreth,et al.  A density functional theory study of the benzene-water complex. , 2008, The journal of physical chemistry. A.

[28]  E. Schröder,et al.  Stacking interactions and the twist of DNA. , 2008, Journal of the American Chemical Society.

[29]  D. Truhlar,et al.  The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals , 2008 .

[30]  O. A. V. Lilienfeld,et al.  Predicting noncovalent interactions between aromatic biomolecules with London-dispersion-corrected DFT. , 2007, The journal of physical chemistry. B.

[31]  A. Becke,et al.  Exchange-hole dipole moment and the dispersion interaction revisited. , 2007, The Journal of chemical physics.

[32]  S. Grimme,et al.  Structure and binding energies of the porphine dimer , 2007 .

[33]  J. Černý,et al.  Non-covalent interactions in biomacromolecules. , 2007, Physical chemistry chemical physics : PCCP.

[34]  A. Becke,et al.  A unified density-functional treatment of dynamical, nondynamical, and dispersion correlations. , 2007, The Journal of chemical physics.

[35]  M. B. Haider,et al.  Self-directed growth of contiguous perpendicular molecular lines on H-Si(100) surfaces. , 2007, The journal of physical chemistry. A.

[36]  C. Cramer,et al.  PAPER www.rsc.org/pccp | Physical Chemistry Chemical Physics Electrochemical impedance spectroscopy of mixed conductors under a chemical potential gradient: a case study of Pt|SDC|BSCF , 2007 .

[37]  S. Chao,et al.  Comparative performance of exchange and correlation density functionals in determining intermolecular interaction potentials of the methane dimer. , 2007, The journal of physical chemistry. A.

[38]  O. A. von Lilienfeld,et al.  Weakly Bonded Complexes of Aliphatic and Aromatic Carbon Compounds Described with Dispersion Corrected Density Functional Theory. , 2007, Journal of chemical theory and computation.

[39]  S. Grimme,et al.  A combined experimental and theoretical study on the conformation of multiarmed chiral aryl ethers. , 2007, The Journal of organic chemistry.

[40]  J. Ángyán.  On the exchange-hole model of London dispersion forces. , 2007, The Journal of chemical physics.

[41]  Stefan Grimme,et al.  Noncovalent Interactions between Graphene Sheets and in Multishell (Hyper)Fullerenes , 2007 .

[42]  S. Grimme,et al.  Double-hybrid density functionals with long-range dispersion corrections: higher accuracy and extended applicability. , 2007, Physical chemistry chemical physics : PCCP.

[43]  Takao Tsuneda,et al.  Long-range corrected density functional study on weakly bound systems: balanced descriptions of various types of molecular interactions. , 2007, The Journal of chemical physics.

[44]  O. A. von Lilienfeld,et al.  Library of dispersion-corrected atom-centered potentials for generalized gradient approximation functionals: Elements H, C, N, O, He, Ne, Ar, and Kr , 2007 .

[45]  A. Goursot,et al.  Interaction between n-Alkane Chains:  Applicability of the Empirically Corrected Density Functional Theory for Van der Waals Complexes. , 2007, Journal of chemical theory and computation.

[46]  P. Hyldgaard,et al.  Van der Waals density functional: Self-consistent potential and the nature of the van der Waals bond , 2007, cond-mat/0703442.

[47]  S. Grimme,et al.  Density functional theory with dispersion corrections for supramolecular structures, aggregates, and complexes of (bio)organic molecules. , 2007, Organic & biomolecular chemistry.

[48]  Jirí Cerný,et al.  Density functional theory augmented with an empirical dispersion term. Interaction energies and geometries of 80 noncovalent complexes compared with ab initio quantum mechanics calculations , 2007, J. Comput. Chem..

[49]  J. Černý,et al.  Resolution of identity density functional theory augmented with an empirical dispersion term (RI-DFT-D): a promising tool for studying isolated small peptides. , 2007, The journal of physical chemistry. A.

[50]  Axel D. Becke,et al.  Van der Waals interactions from the exchange hole dipole moment: Application to bio-organic benchmark systems , 2006 .

[51]  Stefan Grimme,et al.  Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction , 2006, J. Comput. Chem..

[52]  D. Langreth,et al.  Towards a working density-functional theory for polymers: First-principles determination of the polyethylene crystal structure , 2006, cond-mat/0611498.

[53]  S. Grimme,et al.  Density functional theory including dispersion corrections for intermolecular interactions in a large benchmark set of biologically relevant molecules. , 2006, Physical chemistry chemical physics : PCCP.

[54]  M. Gray,et al.  Hexabenzocoronene Model Compounds for Asphaltene Fractions: Synthesis & Characterization , 2006 .

[55]  A. Becke,et al.  A post-Hartree-Fock model of intermolecular interactions: inclusion of higher-order corrections. , 2006, The Journal of chemical physics.

[56]  A. Tkatchenko,et al.  Adsorption of Ar on graphite using London dispersion forces corrected Kohn-Sham density functional theory , 2006 .

[57]  Jirí Cerný,et al.  Benchmark database of accurate (MP2 and CCSD(T) complete basis set limit) interaction energies of small model complexes, DNA base pairs, and amino acid pairs. , 2006, Physical chemistry chemical physics : PCCP.

[58]  G. DiLabio,et al.  Structure and binding energies in van der Waals dimers: Comparison between density functional theory and correlated ab initio methods , 2006 .

[59]  G. DiLabio,et al.  Linear nanostructure formation of aldehydes by self-directed growth on hydrogen-terminated silicon(100). , 2006, The journal of physical chemistry. B.

[60]  Donald G Truhlar,et al.  Design of Density Functionals by Combining the Method of Constraint Satisfaction with Parametrization for Thermochemistry, Thermochemical Kinetics, and Noncovalent Interactions. , 2006, Journal of chemical theory and computation.

[61]  E. Schröder,et al.  Application of van der Waals density functional to an extended system: adsorption of benzene and naphthalene on graphite. , 2006, Physical review letters.

[62]  A. Becke,et al.  Exchange-hole dipole moment and the dispersion interaction: high-order dispersion coefficients. , 2006, The Journal of chemical physics.

[63]  Adrienn Ruzsinszky,et al.  Binding energy curves from nonempirical density functionals II. van der Waals bonds in rare-gas and alkaline-earth diatomics. , 2005, The journal of physical chemistry. A.

[64]  C. David Sherrill,et al.  Beyond the benzene dimer : An investigation of the additivity of π-π interactions , 2005 .

[65]  A. Becke,et al.  A density-functional model of the dispersion interaction. , 2005, The Journal of chemical physics.

[66]  M. Dion,et al.  Binding energies in benzene dimers: Nonlocal density functional calculations. , 2005, The Journal of chemical physics.

[67]  D. Langreth,et al.  Interaction energies of monosubstituted benzene dimers via nonlocal density functional theory. , 2005, The Journal of chemical physics.

[68]  Kimihiko Hirao,et al.  A density-functional study on pi-aromatic interaction: benzene dimer and naphthalene dimer. , 2005, The Journal of chemical physics.

[69]  A. Becke,et al.  A post-Hartree-Fock model of intermolecular interactions. , 2005, The Journal of chemical physics.

[70]  O. A. V. Lilienfeld,et al.  Performance of optimized atom-centered potentials for weakly bonded systems using density functional theory , 2005 .

[71]  A. Becke,et al.  Exchange-hole dipole moment and the dispersion interaction. , 2005, The Journal of chemical physics.

[72]  K. Hirao,et al.  Van der Waals interactions studied by density functional theory , 2005 .

[73]  G. DiLabio,et al.  Dispersion interactions enable the self-directed growth of linear alkane nanostructures covalently bound to silicon. , 2004, Journal of the American Chemical Society.

[74]  Wolfgang Werner Langbein,et al.  Quantum complementarity of microcavity polaritons , 2004, SPIE OPTO.

[75]  Ivano Tavernelli,et al.  Optimization of effective atom centered potentials for london dispersion forces in density functional theory. , 2004, Physical review letters.

[76]  Alexander D. MacKerell.  Empirical force fields for biological macromolecules: Overview and issues , 2004, J. Comput. Chem..

[77]  Stefan Grimme,et al.  Accurate description of van der Waals complexes by density functional theory including empirical corrections , 2004, J. Comput. Chem..

[78]  Robert A. Wolkow,et al.  Application of 25 density functionals to dispersion-bound homomolecular dimers , 2004 .

[79]  Petros Koumoutsakos,et al.  Dispersion corrections to density functionals for water aromatic interactions. , 2004, The Journal of chemical physics.

[80]  M. Dion,et al.  van der Waals density functional for general geometries. , 2004, Physical review letters.

[81]  Gino A. DiLabio,et al.  Density Functional Theory Based Model Calculations for Accurate Bond Dissociation Enthalpies. 3. A Single Approach for X−H, X−X, and X−Y (X, Y = C, N, O, S, Halogen) Bonds , 2003 .

[82]  P. Hyldgaard,et al.  Van der Waals density functional for layered structures. , 2003, Physical review letters.

[83]  David J. Tozer,et al.  Helium dimer dispersion forces and correlation potentials in density functional theory. , 2002 .

[84]  Kimihiko Hirao,et al.  A density functional study of van der Waals interactions , 2002 .

[85]  Weston Thatcher Borden,et al.  Proton-coupled electron transfer versus hydrogen atom transfer in benzyl/toluene, methoxyl/methanol, and phenoxyl/phenol self-exchange reactions. , 2002, Journal of the American Chemical Society.

[86]  Qin Wu,et al.  Empirical correction to density functional theory for van der Waals interactions , 2002 .

[87]  Saroj K. Nayak,et al.  Towards extending the applicability of density functional theory to weakly bound systems , 2001 .

[88]  A. Daniel Boese,et al.  A new parametrization of exchange–correlation generalized gradient approximation functionals , 2001 .

[89]  Thomas Frauenheim,et al.  Hydrogen bonding and stacking interactions of nucleic acid base pairs: A density-functional-theory based treatment , 2001 .

[90]  G. DiLabio,et al.  Predicting the activity of phenolic antioxidants: theoretical method, analysis of substituent effects, and application to major families of antioxidants. , 2001, Journal of the American Chemical Society.

[91]  Fred A. Hamprecht,et al.  Development and assessment of new exchange-correlation functionals , 1998 .

[92]  P. A. Christiansen,et al.  Accurate relativistic effective potentials for the sixth-row main group elements , 1997 .

[93]  Yingkai Zhang,et al.  Describing van der Waals interaction in diatomic molecules with generalized gradient approximations: The role of the exchange functional , 1997 .

[94]  D. Langreth,et al.  Density Functional for van der Waals Forces at Surfaces. , 1996, Physical review letters.

[95]  A. Becke.  Exchange-correlation approximations in density-functional theory. , 1995 .

[96]  José M. Pérez-Jordá,et al.  A density-functional study of van der Waals forces: rare gas diatomics. , 1995 .

[97]  Mark S. Gordon,et al.  General atomic and molecular electronic structure system , 1993, J. Comput. Chem..

[98]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[99]  Jackson,et al.  Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. , 1992, Physical review. B, Condensed matter.

[100]  Axel D. Becke,et al.  Numerical solution of Schrödinger’s equation in polyatomic molecules , 1990 .

[101]  A. Becke.  A multicenter numerical integration scheme for polyatomic molecules , 1988 .

[102]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[103]  Axel D. Becke,et al.  Density Functional Calculations of Molecular Bond Energies , 1986 .

[104]  William J. Meath,et al.  Dispersion energy constants C 6(A, B), dipole oscillator strength sums and refractivities for Li, N, O, H2, N2, O2, NH3, H2O, NO and N2O , 1977 .

[105]  Giacinto Scoles,et al.  Intermolecular forces in simple systems , 1977 .

[106]  John W. Hepburn,et al.  A simple but reliable method for the prediction of intermolecular potentials , 1975 .

[107]  M. Karplus,et al.  Van der Waals Forces in Atoms and Molecules , 1964 .

[108]  L. Salem.  The calculation of dispersion forces , 1960 .

[109]  H. Casimir,et al.  The Influence of Retardation on the London-van der Waals Forces , 1948 .

[110]  John C. Slater,et al.  The Van Der Waals Forces in Gases , 1931 .

[111]  Henrik Rydberg,et al.  Van der Waals Density Functional Theory with Applications , 2005 .

[112]  Ivano Tavernelli,et al.  Variational optimization of effective atom centered potentials for molecular properties. , 2005, The Journal of chemical physics.

[113]  A. Dalgarno,et al.  The Calculation of Van Der Waals Interactions , 1966 .