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Title

Interaction energies in hydrogen-bonded systems: A testing ground for subsystem formulation of density-functional theory

Authors
Dulak, Marcin
Published in Journal of Chemical Physics. 2006, vol. 124, no. 2, p. 24104
Abstract The formalism based on the total energy bifunctional (E[rhoI,rhoII]) is used to derive interaction energies for several hydrogen-bonded complexes (water dimer, HCN–HF, H2CO–H2O, and MeOH–H2O). Benchmark ab initio data taken from the literature were used as a reference in the assessment of the performance of gradient-free [local density approximation (LDA)] and gradient-dependent [generalized gradient approximation (GGA)] approximations to the exchange-correlation and nonadditive kinetic-energy components of E[rhoI,rhoII]. On average, LDA performs better than GGA. The average absolute error of calculated LDA interaction energies amounts to 1.0 kJ/mol. For H2CO–H2O and H2O–H2O complexes, the potential-energy curves corresponding to the stretching of the intermolecular distance are also calculated. The positions of the minima are in a good agreement (less than 0.2 Å) with the reference ab initio data. Both variational and nonvariational calculations are performed to assess the energetic effects associated with complexation-induced deformations of molecular electron densities.
Keywords WaterHydrogen compoundsCarbon compoundsOrganic compoundsHydrogen bondsDensity functional theoryOrbital calculationsPotential energy surfacesVariational techniques
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Research group Groupe Wesolowski
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KEVORKYANTS, Ruslan, DULAK, Marcin, WESOLOWSKI, Tomasz Adam. Interaction energies in hydrogen-bonded systems: A testing ground for subsystem formulation of density-functional theory. In: Journal of Chemical Physics, 2006, vol. 124, n° 2, p. 24104. https://archive-ouverte.unige.ch/unige:3287

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Deposited on : 2009-09-21

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