Journal ArticleDOI
Estimates of the Ab Initio Limit for π−π Interactions: The Benzene Dimer
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TLDR
In this article, the binding energies of the benzene dimer were investigated at the second-order Moller−Plesset perturbation theory (MP2) level, and it was shown that more modest basis sets such as aug-cc-pVDZ are sufficient for geometry optimizations of intermolecular parameters.Abstract:
State-of-the-art electronic structure methods have been applied to the simplest prototype of aromatic π−π interactions, the benzene dimer. By comparison to results with a large aug-cc-pVTZ basis set, we demonstrate that more modest basis sets such as aug-cc-pVDZ are sufficient for geometry optimizations of intermolecular parameters at the second-order Moller−Plesset perturbation theory (MP2) level. However, basis sets even larger than aug-cc-pVTZ are important for accurate binding energies. The complete basis set MP2 binding energies, estimated by explicitly correlated MP2−R12/A techniques, are significantly larger in magnitude than previous estimates. When corrected for higher-order correlation effects via coupled cluster with singles, doubles, and perturbative triples [CCSD(T)], the binding energies De (D0) for the sandwich, T-shaped, and parallel-displaced configurations are found to be 1.8 (2.0), 2.7 (2.4), and 2.8 (2.7) kcal mol-1, respectively.read more
Citations
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Accurate description of van der Waals complexes by density functional theory including empirical corrections
TL;DR: The DFT‐D‐BLYP model seems to be even superior to standard MP2 treatments that systematically overbind, and the approach is suggested as a practical tool to describe the properties of many important van der Waals systems in chemistry.
Journal ArticleDOI
A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions.
Yan Zhao,Donald G. Truhlar +1 more
TL;DR: The new local density functional, called M06-L, is designed to capture the main dependence of the exchange-correlation energy on local spin density, spin density gradient, and spin kinetic energy density, and it is parametrized to satisfy the uniform-electron-gas limit.
Journal ArticleDOI
Improved second-order Møller–Plesset perturbation theory by separate scaling of parallel- and antiparallel-spin pair correlation energies
TL;DR: In this paper, a modification of second-order Moller-plesset perturbation theory (MP2) is proposed to improve the description of molecular ground state energies.
Journal ArticleDOI
Design of density functionals that are broadly accurate for thermochemistry, thermochemical kinetics, and nonbonded interactions.
Yan Zhao,Donald G. Truhlar +1 more
TL;DR: Two new hybrid meta exchange-correlation functionals for thermochemistry, thermochemical kinetics, and nonbonded interactions are developed and it is drawn that the PW6B95, MPW1B 95, B98, B97-1, and TPSS1KCIS methods give the best results for a combination of thermochemistry and non bonding interactions.
Journal ArticleDOI
Supramolecular Binding Thermodynamics by Dispersion-Corrected Density Functional Theory
TL;DR: The theoretical approach employs a (nondynamic) single-structure model, but computes the various energy terms accurately without any special empirical adjustments, and provides unprecedented accuracy for ΔG(a) values with errors of only 2 kcal mol(-1) on average.
References
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Electron affinities of the first-row atoms revisited. Systematic basis sets and wave functions
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The nature of .pi.-.pi. interactions
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Gaussian basis sets for use in correlated molecular calculations. V. Core-valence basis sets for boron through neon
David E. Woon,Thom H. Dunning +1 more
TL;DR: In this article, the correlationconsistent polarized core-valence basis sets (cc•pVXZ) for the atoms boron through neon have been extended to treat core and core•valence correlation effects, and the exponents of the core functions were determined by minimizing the difference between allelectron and valence only correlation energies obtained from HF+1+2 calculations on the ground states of the atoms.