Initiation of explicitly correlated Slater-type geminal theory

Ten‐no, Seiichiro

doi:10.1016/j.cplett.2004.09.041

Cited by 475 publications

(387 citation statements)

References 25 publications

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“…The F12 theory of explicitly correlated calculations is now well established [101] but to apply STOs in such computations several issues of both technical and theoretical nature need to be resolved. For instance, for GTOs calculations the exponential correlation factor of Ten-no [102,103] is nowadays routinely used. In the case of STOs basis sets this choice is not feasible at present, due to an extremely complicated theory of evaluation of the resulting molecular two-electron integrals [104,105].…”

Section: Discussionmentioning

confidence: 99%

Reexamination of the calculation of two-center, two-electron integrals over Slater-type orbitals. III. Case study of the beryllium dimer

et al. 2015

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In this paper we present results of ab-initio calculations for the beryllium dimer with basis set of Slater-type orbitals (STOs). Nonrelativistic interaction energy of the system is determined using the frozen-core full configuration interaction calculations combined with high-level coupled cluster correction for inner-shell effects. Newly developed STOs basis sets, ranging in quality from double to sextuple zeta, are used in these computations. Principles of their construction are discussed and several atomic benchmarks are presented. Relativistic effects of order α 2 are calculated perturbatively by using the Breit-Pauli Hamiltonian and are found to be significant. We also estimate the leading-order QED effects. Influence of the adiabatic correction is found to be negligible. Finally, the interaction energy of the beryllium dimer is determined to be 929.0 ± 1.9 cm −1 , in a very good agreement with the recent experimental value. The results presented here appear to be the most accurate ab-initio calculations for the beryllium dimer available in the literature up to date and probably also one of the most accurate calculations for molecular systems containing more than four electrons.

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Section: Discussionmentioning

confidence: 99%

Reexamination of the calculation of two-center, two-electron integrals over Slater-type orbitals. III. Case study of the beryllium dimer

et al. 2015

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“…109,110 In the explicitly correlated calculations, we used a Slater type correlation factor as proposed by Ten-no. 111 In Turbomole, the Slater type function is represented by a linear combination of six Gaussians. 112 For the larger clusters of up to 72 atoms, we applied the incremental scheme 113-115 using a third order expansion, 116,117 the domain-specific basis set, 116,118 a distance-screening for small increments, 119,120 and a MP2 based error correction.…”

Section: Quantum Chemical Methods and Qce Protocolmentioning

confidence: 99%

Quantum cluster equilibrium model of N-methylformamide–water binary mixtures

Domaros

Jähnigen

Friedrich

et al. 2016

The Journal of Chemical Physics

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The established quantum cluster equilibrium (QCE) approach is refined and applied to Nmethylformamide (NMF) and its aqueous solution. The QCE method is split into two iterative cycles: one which converges to the liquid phase solution of the QCE equations and another which yields the gas phase. By comparing Gibbs energies, the thermodynamically stable phase at a given temperature and pressure is then chosen. The new methodology avoids metastable solutions and allows a different treatment of the mean-field interactions within the gas and liquid phases. These changes are of crucial importance for the treatment of binary mixtures. For the first time in a QCE study, the cis-trans-isomerism of a species (NMF) is explicitly considered. Cluster geometries and frequencies are calculated using density functional theory (DFT) and complementary coupled cluster single point energies are used to benchmark the DFT results. Independent of the selected quantum-chemical method, a large set of clusters is required for an accurate thermodynamic description of the binary mixture. The liquid phase of neat NMF is found to be dominated by the cyclic trans-NMF pentamer, which can be interpreted as a linear trimer that is stabilized by explicit solvation of two further NMF molecules. This cluster reflects the known hydrogen bond network preferences of neat NMF. C 2016 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license

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“…The basis set error correction was evaluated also in the periodic framework, employing the recently implemented periodic LMP2-F12 method [36] in the 3 * A fixed-amplitude approximation [49][50][51]. The periodic F12 correction was evaluated using a three-layer MgO slab.…”

Section: Appendix D: Incremental Ccsd(t) Correction To the Periodic Lmentioning

confidence: 99%

Approaching an exact treatment of electronic correlations at solid surfaces: The binding energy of the lowest bound state of helium adsorbed on MgO(100)

et al. 2014

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In this work we employ ab initio electronic structure theory at a very high level to resolve a long standing experimental controversy; the interaction between helium and the MgO (100) surface has been studied extensively by other groups, employing diverse experimental approaches. Nevertheless, the binding energy of the lowest bound state is still unclear: the existence of a state at around −5.5 meV is well established but a state at −10 meV has also been reported. The MgO (100)-He system captures the fundamental physics involved in many adsorption problems; the weak binding is governed by long-range electronic correlation for which a fully predictive theory applicable to the solid state has been elusive. The above-mentioned experimental controversy can now be resolved on the basis of the calculations presented in this work. We performed three-dimensional vibrational dynamics calculations on a highly accurate potential-energy surface. The latter was constructed using a method which systematically approaches the exact limit in its treatment of electronic correlation. The outcome is clear: our calculations do not support the existence of a bound state around −10 meV. The interaction between molecules and crystalline surfaces is of great fundamental and technological interest and is extensively studied both experimentally and theoretically [1][2][3]. One particular example is physisorption and scattering of helium atoms on oxide surfaces. In the last two decades the latter process, employing molecular-beam techniques, has been developed into a powerful tool for the analysis of surface structure and dynamics [4][5][6][7][8]. It is particularly useful for studying insulating surfaces, such as MgO [4,9]. At close proximity the helium-surface interaction potential is dominated by the exponentially growing corrugated repulsive wall, which is a consequence of the mutual exchange repulsion between the helium and surface electron densities. The repulsive potential is two-dimensional (2D) corrugated and leads to a complicated diffraction pattern for helium scattered from the surface. In the range of intermediate He-surface distances, there exists a very shallow attractive potential due to the weak van der Waals interactions, which drops off with distance from the surface as 1/z 3 [10]. Such a potential can support several bound states (in fact several 2D bands of bound states), which correspond to vibrational levels of helium atoms physisorbed on the surface.The delicacy of the balance between different components of the helium-surface interaction makes quantitatively accurate theoretical predictions of the behavior of helium atoms on the surface extremely difficult. Standard density functional theory (DFT), which is the common tool in solid-state simulations (i.e., local-density approximation, generalized gradient approximation, or hybrids), does not capture van der Waals dispersion. In principle it can be used for calculating * r.martinezcasado@imperial.ac.uk † denis.usvyat@chemie.uni-regensburg.de the repulsive wall at th...

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Initiation of explicitly correlated Slater-type geminal theory

Cited by 475 publications

References 25 publications

Reexamination of the calculation of two-center, two-electron integrals over Slater-type orbitals. III. Case study of the beryllium dimer

Reexamination of the calculation of two-center, two-electron integrals over Slater-type orbitals. III. Case study of the beryllium dimer

Quantum cluster equilibrium model of N-methylformamide–water binary mixtures

Approaching an exact treatment of electronic correlations at solid surfaces: The binding energy of the lowest bound state of helium adsorbed on MgO(100)

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