Tutorial 3: van der Waals...
Transcript of Tutorial 3: van der Waals...
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Tutorial 3:van der Waals Interactions
Jan Hermann Alexandre TkatchenkoFritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin
Hands-On Summer SchoolLos Angeles, July 24, 2014
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Pairwise approaches to van der Waals
Interatomic methods Non-local functionals
• Grimme'sDFT-Dn1
• Tkatchenko–Scheffler2 C� functionals of density
+ Fast,simple − Atomic parameters input − Problems with metals and
charge-transfer character
• Langreth–Lundqvist3
• Vydrov–vanVoorhis4
+ Pure density functionals − Questionable for
molecules,metals
1Grimme, J. Comp. Chem. (2004) 2Tkatchenko, Scheffler, Phys. Rev. Lett. (2009)3Dion, Phys. Rev. Lett. (2004) 4Vydrov, van Voorhis, Phys. Rev. Lett (2004)
? n(r�)Φ[n](r�, r�)n(r�)dr�dr�∑i< j
f (Ri j)C6,i j[n]R6i j
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How to go beyond pairwise van der Waals
Many-body dispersion1 EXX+RPA@DFT2
• χ� from localized atomic response functions
• Basedondipoleharmonicoscillators
+ Can be solved analytically − Open problem with metals
• χ� from delocalized molecular orbitals
+ Works for all sorts of systems − Costly numerical solution
1Tkatchenko, DiStasio, Car, Scheffler, Phys. Rev. Lett. (2012)2Zhu, Toulouse, Savin, Ángyán, J. Chem. Phys. (2010) and refs therein
• Random-phaseapproximation(RPA)framework
Ec = −��π
=ô
�dω
ô
9n=�
�n Tr[(χ�V )n]
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BenzeneisabuildingelementofmanyvdWsystems
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Frombenzenemoleculetographite
• Benzenemolecule• Benzenedimer• Benzenecrystal• Benzenechain• Benzeneongraphene• Graphenebilayer• Graphenemultilayer
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3
2 α̃ = α αT<Rα̃
1
How many-body dispersion works
Self-consistentscreening• Responsefunctionsofnear
atoms interact
• Eachatomreplacedbyoscillator with α from Tkatchenko–Scheffler
Random-phase approx• Givesthelong-rangevan
der Waals energy• Solvedanalytically
Ec = −12π
∫∞
0dω
∞
∑n=2
1n Tr[(α̃T>R)n]
α = αfreeV[n]Vfree
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Non-empirical vdW methods provide more info
• noinformationbeyondenergy
• polarizability• anisotropy• dipolefluctuationmodes
Fromempirical... ...tofirstprinciples
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Structureisthestartingpointofmostcalculations
• Localminimaonthepotential energy surface
• Transitionstates• Equilibriumstructure
(globalminimum)
Benzenedimer• TestcaseforvanderWaals
for decades• StrongvdWinteractions• Quadrupole–quadrupole
interactions• Stronganisotropy
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Many-body effects get interesting in crystals
• Many-bodyeffectsgetamplified• Multipledirectionsofinteraction• Anisotropy
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Emergenceoflong-rangefluctuationsinlow-dimensional systems• Ittakeslongerdistancesbeforemany-bodyeffectsgetsaturated• 2Dsystems:physisorption,interfaces• 1Dsystems:self-assembly,quantumwires