On the importance of the fragment relaxation energy terms in the estimation of the basis set superposition error correction to the intermolecular interaction energy

The formalism based on the total energy bifunctional ͑E͓ I , II ͔͒ is used to derive interaction energies for several hydrogen-bonded complexes ͑water dimer, HCN-HF, H 2 CO-H 2 O, and MeOH -H 2 O͒. 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 ͑LDA͔͒ and gradient-dependent ͓generalized gradient approximation ͑GGA͔͒ approximations to the exchange-correlation and nonadditive kinetic-energy components of E͓ I , II ͔. On average, LDA performs better than GGA. The average absolute error of calculated LDA interaction energies amounts to 1.0 kJ/ mol. For H 2 CO-H 2 O and H 2 O-H 2 O 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 Å͒ 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.

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“…24 Below, we follow the notation from Ref. 22: ͑i͒ the electronic energy of a molecular system M at geometry G computed with basis set…”

Section: Resultsmentioning

confidence: 99%

“…Nevertheless, the effect of this geometrical relaxation on the interaction energies is known to be rather small in the case of weak hydrogen bonds ͑0.4 kJ/ mol in the case of water dimer, for instance͒. 22,23 …”

Section: Computational Detailsmentioning

confidence: 99%

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

Kevorkyants

Dułak

Wesołowski

2006

The Journal of Chemical Physics

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“…The H-bond enthalpy of the dimer is 25.9 kJ/mol, and about a fifth of this energy is due to polarization. High-level QM calculations indicate a smaller bond enthalpy (20.50 kJ/mol [43]), which is typically overestimated by empirical models ( Table 2). The fit for the protonated dimer (Zundel) has an rOO of 2.42 Å, and the excess proton is approximately equidistant from the two oxygens (Fig.…”

Section: Monomers: Water Hydronium and Hydroxidementioning

confidence: 99%

Lewis-inspired representation of dissociable water in clusters and Grotthuss chains

et al. 2011

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Proton transfer to and from water is critical to the function of water in many settings. However, it has been challenging to model. Here, we present proof-of-principle for an efficient yet robust model based on Lewis-inspired submolecular particles with interactions that deviate from Coulombic at short distances to take quantum effects into account. This "LEWIS" model provides excellent correspondence with experimental structures for water molecules and water clusters in their neutral, protonated and deprotonated forms, reasonable values for the proton affinities of water and hydroxide, a good value for the strength of the hydrogen bond in the water dimer, the correct order of magnitude for the stretch and bend force constants of water, and the expected time course for Grotthuss transport in water chains.

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“…[5][6][7][8] Therefore, for a proper location of the stationary points on a corrected PES, the BSSEcorrection term must be taken into account at every step of the optimization procedure. 5 The most common procedure to correct the single-point interaction energy for BSSE has been the a posteriori counterpoise correction scheme ͑CP correction͒ proposed by Boys and Bernardi.…”

Section: Introductionmentioning

confidence: 99%

C–H⋯O H-bonded complexes: How does basis set superposition error change their potential-energy surfaces?

Salvador

Simon

Duran

et al. 2000

The Journal of Chemical Physics

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Geometries, vibrational frequencies, and interaction energies of the CNH¯O 3 and HCCH¯O 3 complexes are calculated in a counterpoise-corrected ͑CP-corrected͒ potential-energy surface ͑PES͒ that corrects for the basis set superposition error ͑BSSE͒. Ab initio calculations are performed at the Hartree-Fock ͑HF͒ and second-order Mo "ller-Plesset ͑MP2͒ levels, using the 6-31G(d,p) and D95ϩϩ(d, p) basis sets. Interaction energies are presented including corrections for zero-point vibrational energy ͑ZPVE͒ and thermal correction to enthalpy at 298 K. The CP-corrected and conventional PES are compared; the uncorrected PES obtained using the larger basis set including diffuse functions exhibits a double well shape, whereas use of the 6-31G(d,p) basis set leads to a flat single-well profile. The CP-corrected PES has always a multiple-well shape. In particular, it is shown that the CP-corrected PES using the smaller basis set is qualitatively analogous to that obtained with the larger basis sets, so the CP method becomes useful to correctly describe large systems, where the use of small basis sets may be necessary.

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On the importance of the fragment relaxation energy terms in the estimation of the basis set superposition error correction to the intermolecular interaction energy

Cited by 661 publications

References 28 publications

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

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

Lewis-inspired representation of dissociable water in clusters and Grotthuss chains

C–H⋯O H-bonded complexes: How does basis set superposition error change their potential-energy surfaces?

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