Segmented contracted basis sets for atoms H through Xe: Sapporo-(DK)-nZP sets (n = D, T, Q)

Noro, Takeshi; Sekiya, Masahiro; Koga, Toshikatsu

doi:10.1007/s00214-012-1124-z

Cited by 297 publications

(227 citation statements)

References 37 publications

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“…These polarization functions can be combined with an arbitrary HF basis set and have been reported for most of the periodic table, [145][146][147][148][149] including sets for core-valence correlation, [150] and relativistic effects using a DKH Hamiltonian. [151][152][153][154][155] The NOSeC bases typically recover more than 99% of the correlation energy calculated using the parent NOs, but are significantly more computationally efficient.…”

Section: Polarization Consistent Basis Setsmentioning

confidence: 99%

“…[149] Recently, the Sapporo-nZP (n ¼ D, T, Q) have been developed using a similar fitting to reference NOs approach. [157,158] Unlike the NOSeC bases, Sapporo-nZP specify an underlying HF set and core correlating functions are available for all elements (with the obvious exceptions of H and He). For the heavier elements, relativistic effects are considered through a DKH Hamiltonian.…”

Section: Polarization Consistent Basis Setsmentioning

confidence: 99%

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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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Section: Polarization Consistent Basis Setsmentioning

confidence: 99%

Section: Polarization Consistent Basis Setsmentioning

confidence: 99%

Gaussian basis sets for molecular applications

Hill¹

2012

Int J of Quantum Chemistry

188

155

View full text Add to dashboard Cite

show abstract

“…Although we did not explicitly consider a 6p-like orbital, it is represented by p correlating functions for the 6s electrons. In the optimization of the contraction coefficients and orbital exponents, we used the conjugate directions algorithm [20] as before [1]. In Table 2, we show the sum of core and valence correlation energies together with its reproduction rate relative to the corresponding sum by the accurate standard sets.…”

Section: Optimization Of the Segmented Sapporo-nzp Setsmentioning

confidence: 99%

“…In the present paper, we construct relativistic DZP, TZP, and QZP contracted (C) Gaussian-type function (GTF) basis sets for the 15 lanthanide atoms 57 La through 71 Lu as a member of the Sapporo-DK-nZP sets [1] for atoms, where the relativistic effects are considered through the third order of Douglas-Kroll-Hess approximation (DK3) [2,3] and the correlations are considered not only for valence electrons but also for core electrons of the second outermost s and p subshells in the s-and d-block elements, and of the second outermost s, p, and d subshells in the p-block elements. These basis sets show high performance and effectiveness which stem from the adoption of the segmented contraction scheme.…”

Section: Introductionmentioning

confidence: 99%

Relativistic segmented contraction basis sets with core-valence correlation effects for atoms 57La through 71Lu: Sapporo-DK-nZP sets (n = D, T, Q)

et al. 2012

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For the 15 lanthanide atoms 57 La through 71 Lu, we report Sapporo-DK-nZP sets (n = D, T, Q), which are natural extensions of the Sapporo-(DK)-nZP sets for lighter atoms and efficiently incorporate the correlation among electrons in the N through P shells as well as the relativistic effect. The present sets well describe the correlation among the 4s and 4p electrons, which are important in the excitation of 4f electrons. Atomic test calculations of 57 La, 58 Ce, 59 Pr, and 60 Nd at configuration interaction with the Davidson correction level of theory confirm high performance of the present basis sets. Molecular test calculations are carried out for 57 LaF and 70 YbF diatomics at the coupled cluster level of theory. The calculated spectroscopic constants approach smoothly to the experimental values as the quality of the basis set increases.

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“…[29] In addition, we used some diffuse and polarization functions from the Sapporo basis sets. [30] All of the basis sets were used in the uncontracted form. The QZ basis is the most accurate among the ones considered and its accuracy has been confirmed by Gomes et al [28] The bond length and harmonic frequency they obtained with the QZ basis were 2.0196 Å and 503.2 cm −1 , respectively.…”

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confidence: 99%

Application of relativistic coupled-cluster theory to the effective electric field in YbF

et al. 2014

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An accurate determination of the effective electric field (E eff ) in YbF is important, as it can be combined with the results of future experiments to give an improved new limit for the electric dipole moment of the electron. We report a relativistic coupled-cluster calculation of this quantity in which all the core electrons were excited. It surpasses the approximations made in the previous reported calculations. We obtain a value of 23.1 GV/cm for E eff in YbF with an estimated error of less than 10%. The crucial roles of the basis sets and the core excitations in our work are discussed.The electric dipole moment (EDM) of a nondegenerate system arises from violations of both the parity (P) and the time-reversal (T) symmetries [1]. T violation implies charge parity (CP) violation via CPT theorem [2]. In general, CP violation is a necessary condition for the existence of the EDMs of physical systems, and, in particular, atoms and molecules. Paramagnetic atoms and molecules are sensitive to the EDM of the electron (eEDM) [3], which is an important probe of the physics beyond the standard model [4]. The eEDM arising from CP violation could also be related to the matter-antimatter asymmetry in the universe [5]. A number of studies using atoms have been performed during the past few decades to extract an upper limit for the eEDM [6]. In general, for heavy polar molecules, the effective electric field experienced by an electron (E eff ) obtained from relativistic molecular calculations can be several orders of magnitude larger than that in atoms [7]. Therefore, the experimental observable (i.e., the shift in energy because of the interaction of the electric field with the eEDM) is also several orders of magnitude larger. Owing to the high sensitivity of the eEDM in molecules, there has been a considerable increase in interest in this field during the past decade The aim of the present work is to calculate E eff in YbF using a rigorous relativistic many-body method, which is more accurate than the methods used in the previous calculations. The method we have chosen is the four-component relativistic coupled-cluster (RCC) method, which is arguably the current gold standard for calculating the electronic structure of heavy atoms and diatomic molecules [18].The electron EDM interaction Hamiltonian in a molecule can be written as [19] Here, d e is the eEDM of an electron,  is one of the Dirac matrices, and  are the Pauli spin matrices. i is the index of summation labelling for electrons and N e is the total number of electrons. E int is the electric field acting on an electron in a molecule. The quantity that is of experimental interest in the search for the eEDM is an energy shift (E) of a particular state owing to the interaction Hamiltonian given in Eq.(1). This can be expressed as

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Segmented contracted basis sets for atoms H through Xe: Sapporo-(DK)-nZP sets (n = D, T, Q)

Cited by 297 publications

References 37 publications

Gaussian basis sets for molecular applications

Gaussian basis sets for molecular applications

Relativistic segmented contraction basis sets with core-valence correlation effects for atoms 57La through 71Lu: Sapporo-DK-nZP sets (n = D, T, Q)

Application of relativistic coupled-cluster theory to the effective electric field in YbF

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