Optimized accurate auxiliary basis sets for RI-MP2 and RI-CC2 calculations for the atoms Rb to Rn

Hellweg, Arnim; Hättig, Christof; Höfener, Sebastian; Klopper, Wim

doi:10.1007/s00214-007-0250-5

Cited by 691 publications

(529 citation statements)

References 31 publications

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“…55,56 For the MP2 and LCCSD(T0) calculations, we used the cc-pVTZ/MP2FIT (def2-TZVPP MP2 for Mo) or aug-cc-pVQZ/MP2FIT (def2-QZVPP MP2 for Mo) fitting basis sets, respectively. 57,58 The orbitals in the local correlation calculations were obtained through Pipek-Mezey localization. 59 The domains were determined according to the NPA criterion, with T NPA = 0.03.…”

Section: Computational Detailsmentioning

confidence: 99%

Large Density-Functional and Basis-Set Effects for the DMSO Reductase Catalyzed Oxo-Transfer Reaction

Mata

Ryde

2013

J. Chem. Theory Comput.

105

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The oxygen-atom transfer reaction catalyzed by the mononuclear molybdenum enzyme dimethyl sulfoxide reductase (DMSOR) has attracted considerable attention by both experimental and theoretical studies. We show here that this reaction is more sensitive to details of quantum mechanical calculations that what has previously been appreciated. Basis sets of at least triplezeta quality are needed to obtain qualitatively correct results. Dispersion has an appreciable effect on the reaction, in particular the binding of the substrate or the dissociation of the product (up to 34 kJ/mol). Polar and non-polar solvation effects are also significant, especially if the enzyme can avoid cavitation effects by using a pre-formed active-site cavity. Relativistic effects are considerable (up to 22 kJ/mol), but they are reasonably well treated by a relativistic effective core potential. Various density-functional methods give widely different results for the activation and reaction energy (differences of over 100 kJ/mol), mainly reflecting the amount of exact exchange in the functional, owing to the oxidation of Mo from +IV to +VI. By calibration towards local CCSD(T0) calculations, we show that none of eight tested functionals (TPSS, BP86, BLYP, B97-D, TPSSH, B3LYP, PBE0, and BHLYP) give accurate energies for all states in the reaction. Instead, B3LYP gives the best activation barrier, whereas pure functionals give more accurate energies for the other states. Our best results indicate that the enzyme follows a two-step associative reaction mechanism with an overall activation enthalpy of 63 kJ/mol, which is in excellent agreement with the experimental results.

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Section: Computational Detailsmentioning

confidence: 99%

Large Density-Functional and Basis-Set Effects for the DMSO Reductase Catalyzed Oxo-Transfer Reaction

Mata

Ryde

2013

J. Chem. Theory Comput.

105

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“…[186] The development of ABSs for DF-MP2 was greatly streamlined by the introduction of a driver program that uses analytic gradients for the optimization of ABSs within the RICC2 module of the TURBOMOLE package. [121,187] This means that MP2 fitting ABSs (often referred to as ' 'MP2-fit'') have been produced that are specifically matched to correlation consistent and def2 OBSs for most of the periodic table, [95,185,[187][188][189][190][191][192][193] with the advent of explicitly correlated and local electron correlation methods (that use DF) a strong driving force for this development. The resulting ABSs typically contain between two and four times as many functions as the OBS they are matched to, and the fitting errors are two to four orders of magnitude smaller than the incompleteness errors in the OBS.…”

Section: Auxiliary Basis Setsmentioning

confidence: 99%

Gaussian basis sets for molecular applications

Hill¹

2012

Int J of Quantum Chemistry

188

155

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The choice of basis set in quantum chemical calculations can have a huge impact on the quality of the results, especially for correlated ab initio methods. This article provides an overview of the development of Gaussian basis sets for molecular calculations, with a focus on four popular families of modern atom-centered, energy-optimized bases: atomic natural orbital, correlation consistent, polarization consistent, and def2. The terminology used for describing basis sets is briefly covered, along with an overview of the auxiliary basis sets used in a number of integral approximation techniques and an outlook on possible future directions of basis set design.

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“…[27][28][29][30] For accurate LMP2 calculations, a number of technical keywords have to be carefully considered for the Hartree-Fock step, WF generation, and the actual LMP2 step. In all steps, a shrinking factor of 4 (SHRINK) was used to generate a Monkhorst-Pack-type grid of k-points in the reciprocal space, resulting in 8 k-points in the irreducible Brillouin zone of the clathrate-II structure.…”

Section: Methodsmentioning

confidence: 99%

Semiconducting Clathrates Meet Gas Hydrates: Xe₂₄[Sn₁₃₆]

Karttunen

Fässler

2014

Chemistry A European J

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Optimized accurate auxiliary basis sets for RI-MP2 and RI-CC2 calculations for the atoms Rb to Rn

Cited by 691 publications

References 31 publications

Large Density-Functional and Basis-Set Effects for the DMSO Reductase Catalyzed Oxo-Transfer Reaction

Large Density-Functional and Basis-Set Effects for the DMSO Reductase Catalyzed Oxo-Transfer Reaction

Gaussian basis sets for molecular applications

Semiconducting Clathrates Meet Gas Hydrates: Xe₂₄[Sn₁₃₆]

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Optimized accurate auxiliary basis sets for RI-MP2 and RI-CC2 calculations for the atoms Rb to Rn

Cited by 691 publications

References 31 publications

Large Density-Functional and Basis-Set Effects for the DMSO Reductase Catalyzed Oxo-Transfer Reaction

Large Density-Functional and Basis-Set Effects for the DMSO Reductase Catalyzed Oxo-Transfer Reaction

Gaussian basis sets for molecular applications

Semiconducting Clathrates Meet Gas Hydrates: Xe24[Sn136]

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Product

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Semiconducting Clathrates Meet Gas Hydrates: Xe₂₄[Sn₁₃₆]