Basis-set superposition errors in tightly bound systems

Parasuk, Vudhichai; Almlöf, J.; DeLeeuw, Bradley J.

doi:10.1016/0009-2614(91)90001-p

Cited by 17 publications

(4 citation statements)

References 10 publications

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“…Finally, we considered basis set superposition error (BSSE). Among the different manybody generalizations [42,43,44] of the counterpoise correction [45], we have followed the 'site-site function counterpoise' definition of Wells and Wilson [42]. The results are given in Table VI.…”

Section: Improved Scalar Relativistic Correctionmentioning

confidence: 99%

W3 theory: Robust computational thermochemistry in the kJ/mol accuracy range

Boese

Oren

Atasoylu

et al. 2004

The Journal of Chemical Physics

463

449

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We are proposing a new computational thermochemistry protocol denoted W3 theory, as a successor to W1 and W2 theory proposed earlier [Martin and De Oliveira, J. Chem. Phys. 111, 1843 (1999)]. The new method is both more accurate overall (error statistics for total atomization energies approximately cut in half) and more robust (particularly towards systems exhibiting significant nondynamical correlation) than W2 theory. The cardinal improvement rests in an approximate account for post-CCSD(T) correlation effects. Iterative T3 (connected triple excitations) effects exhibit a basis set convergence behavior similar to the T3 contribution overall. They almost universally decrease molecular binding energies. Their inclusion in isolation yields less accurate results than CCSD(T) nearly across the board: It is only when T4 (connected quadruple excitations) effects are included that superior performance is achieved. T4 effects systematically increase molecular binding energies. Their basis set convergence is quite rapid, and even CCSDTQ/cc-pVDZ scaled by an empirical factor of 1.2532 will yield a quite passable quadruples contribution. The effect of still higher-order excitations was gauged for a subset of molecules (notably the eight-valence electron systems): T5 (connected quintuple excitations) contributions reach 0.3 kcal/mol for the pathologically multireference X 1Sigmag+ state of C2 but are quite small for other systems. A variety of avenues for achieving accuracy beyond that of W3 theory were explored, to no significant avail. W3 thus appears to represent a good compromise between accuracy and computational cost for those seeking a robust method for computational thermochemistry in the kJ/mol accuracy range on small systems.

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Section: Improved Scalar Relativistic Correctionmentioning

confidence: 99%

W3 theory: Robust computational thermochemistry in the kJ/mol accuracy range

Boese

Oren

Atasoylu

et al. 2004

The Journal of Chemical Physics

463

449

View full text Add to dashboard Cite

show abstract

“…Note that the corresponding energy values can be influenced by basis set superposition error (BSSE) 59 and zero-point energy corrections. It is difficult to assess BSSE unambiguously, and in a consistent manner, for both pathways. One may reasonably expect, however, that these corrections would be quite similar for both pathways.…”

Section: Referencesmentioning

confidence: 99%

Mechanistic Aspects of the Rhodium-Catalyzed Hydrogenation of CO₂ to Formic AcidA Theoretical and Kinetic Study^,

et al. 1997

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The mechanism of the rhodium-catalyzed hydrogenation of CO2 to formic acid was investigated by initial rate measurements using the complex [(dppp)Rh(hfacac)] (A) (dppp = Ph2P(CH2)3PPh2, hfacac = hexafluoroacetylacetonate) as a catalyst precursor in DMSO/NEt3 and by ab initio calculations using cis-[(H3P)2Rh] as a model fragment for the catalytically active site. The kinetic data are consistent with a mechanism that involves rate limiting product formation by liberation of formic acid from an intermediate that is formed via two reversible reactions of the actual catalytically active species first with CO2 and then with H2. The calculations provide for the first time a theoretical analysis of the full catalytic cycle of CO2 hydrogenation. They give detailed insight into the structure of possible intermediates and their transformations during the individual steps. The results suggest σ-bond metathesis as an alternative low energy pathway to a classical oxidative addition/reductive elimination sequence for the reaction of the formate intermediate with dihydrogen.

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“…This concern is fully justified in view of current interest in intermolecular interactions since the nonphysical effects of BSSE can seriously distort the quantitative and qualitative results of calculations on both weakly bound (van der Waals) [3] and tightly bound (covalent) [4] systems.…”

Section: Introductionmentioning

confidence: 99%

Some comments on the counterpoise correction for the basis set superposition error at the correlated level

Cook

Sordo

1993

Int J of Quantum Chemistry

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The use of the counterpoise method for the mitigation of basis set superposition error at the correlated level is discussed. Evidence is presented to show that the ghost basis plays a dual role in the counterpoise method: The orbitals of the system are improved by the ghost basis but at the expense of a nonphysical increase in the dimension of the virtual space. This second factor has no effect on application of the counterpoise method at the SCF level but it makes the use of the counterpoise method at the correlated level much less straightforward.

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Basis-set superposition errors in tightly bound systems

Cited by 17 publications

References 10 publications

W3 theory: Robust computational thermochemistry in the kJ/mol accuracy range

W3 theory: Robust computational thermochemistry in the kJ/mol accuracy range

Mechanistic Aspects of the Rhodium-Catalyzed Hydrogenation of CO₂ to Formic AcidA Theoretical and Kinetic Study^,

Some comments on the counterpoise correction for the basis set superposition error at the correlated level

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Basis-set superposition errors in tightly bound systems

Cited by 17 publications

References 10 publications

W3 theory: Robust computational thermochemistry in the kJ/mol accuracy range

W3 theory: Robust computational thermochemistry in the kJ/mol accuracy range

Mechanistic Aspects of the Rhodium-Catalyzed Hydrogenation of CO2 to Formic AcidA Theoretical and Kinetic Study,

Some comments on the counterpoise correction for the basis set superposition error at the correlated level

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Mechanistic Aspects of the Rhodium-Catalyzed Hydrogenation of CO₂ to Formic AcidA Theoretical and Kinetic Study^,