Gaussian basis sets for use in correlated molecular calculations. XI. Pseudopotential-based and all-electron relativistic basis sets for alkali metal (K–Fr) and alkaline earth (Ca–Ra) elements

Hill, Jimmy; Peterson, Kirk A.

doi:10.1063/1.5010587

Cited by 183 publications

(153 citation statements)

References 74 publications

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“…where c and d are other fit parameters. The basis set used in extrapolation is uncontracted aug-cc-pwCVnZ [21,22] where n=(T, Q, 5). We also evaluated the errors of other established ECPs so as to demonstrate the degree of improvement in our ccECP pseudopotentials.…”

Section: Resultsmentioning

confidence: 99%

A new generation of effective core potentials from correlated calculations: 4s and 4p main group elements and first row additions

Wang

Annaberdiyev

Melton

et al. 2019

The Journal of Chemical Physics

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Recently, we developed a new method for generating effective core potentials (ECPs) using valence energy isospectrality with explicitly correlated all-electron (AE) excitations and norm-conservation criteria. We apply this methodology to the 3 rd -row main group elements, creating new correlation consistent effective core potentials (ccECPs) and also derive additional ECPs to complete the ccECP table for H-Kr. For K and Ca, we develop Ne-core ECPs and for the 4p main group elements, we construct [Ar]3d 10 -core potentials. Scalar relativistic effects are included in their construction. Our ccECPs reproduce AE spectra with significantly better accuracy than many existing pseudopotentials and show better overall consistency across multiple properties. The transferability of ccECPs is tested on monohydride and monoxide molecules over a range of molecular geometries. For the constructed ccECPs we also provide optimized DZ -6Z valence Gaussian basis sets.2. We use a simple and minimal parameterization for the ECP. The ccECPs are expressed in a wellestablished functional form [12] that is captured by arXiv:1907.08658v1 [cond-mat.mtrl-sci]

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Section: Resultsmentioning

confidence: 99%

A new generation of effective core potentials from correlated calculations: 4s and 4p main group elements and first row additions

Wang

Annaberdiyev

Melton

et al. 2019

The Journal of Chemical Physics

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“…The total energy was optimised with a convergence threshold of 10 −7 E h in all cases, using in-house electronic structure software. This was done separately using diffuse augmented correlation consistent, aug-cc-pVx Z (aVx Z), basis sets for all atoms, [45][46][47][48][49][50] with x = D, T. The evaluation of spectroscopic constants for the group 1 elements was carried out using augmented weighted core-valence sets, aug-cc-pwCVDZ-PP (awCVDZ), [50], with the core electrons correlated in the coupled cluster calculations. All sets for the elements K, Rb and Cs were paired with the small-core relativistic pseudopotentials of Lim et al [51] All further interaction energy calculations were performed at the CCSD(T) or CCSD(T)- .…”

Section: Optimisation Proceduresmentioning

confidence: 99%

Midbond basis functions for weakly bound complexes

Shaw

Hill

2018

Molecular Physics

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Weakly bound systems present a difficult problem for conventional atom-centred basis sets due to large separations, necessitating the use of large, computationally expensive bases. This can be remedied by placing a small number of functions in the region between molecules in the complex. We present compact sets of optimised midbond functions for a range of complexes involving noble gases, alkali metals, and small molecules for use in high accuracy coupled cluster calculations, along with a more robust procedure for their optimisation. It is shown that excellent results are possible with double-zeta quality orbital basis sets when a few midbond functions are added, improving both the interaction energy and the equilibrium bond lengths of a series of noble gas dimers by 47 and 8%, respectively. When used in conjunction with explicitly correlated methods, near complete basis set limit accuracy is readily achievable at a fraction of the cost that using a large basis would entail. General purpose auxiliary sets are developed to allow explicitly correlated midbond function studies to be carried out, making it feasible to perform very high accuracy calculations on weakly bound complexes.

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“…Indeed, most commonly used quantum chemistry programs, such as Refs. to name a few, employ Gaussian basis sets such as the Pople 6‐31G and 6‐311G series, the Karlsruhe def and def2 series, the correlation consistent cc‐pVXZ series by Dunning, Peterson, and coworkers, the polarization consistent pc‐ n and pcseg‐ n series by Jensen, the n ZaPa sets by Petersson and coworkers, as well as the atomic natural orbital (ANO) basis sets by Almlöf, Roos, and coworkers; see, for example, Refs. for reviews on Gaussian basis sets.…”

Section: Lcao Approachesmentioning

confidence: 99%

A review on non‐relativistic, fully numerical electronic structure calculations on atoms and diatomic molecules

Lehtola

2019

Int J of Quantum Chemistry

102

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The need for accurate calculations on atoms and diatomic molecules is motivated by the opportunities and challenges of such studies. The most commonly used approach for all-electron electronic structure calculations in general-the linear combination of atomic orbitals (LCAO) method-is discussed in combination with Gaussian, Slater a.k.a. exponential, and numerical radial functions. Even though LCAO calculations have major benefits, their shortcomings motivate the need for fully numerical approaches based on, for example, finite differences, finite elements, or the discrete variable representation, which are also briefly introduced. Applications of fully numerical approaches for general molecules are briefly reviewed, and their challenges are discussed. It is pointed out that the high level of symmetry present in atoms and diatomic molecules can be exploited to fashion more efficient fully numerical approaches for these special cases, after which it is possible to routinely perform allelectron Hartree-Fock and density functional calculations directly at the basis set limit on such systems. Applications of fully numerical approaches to calculations on atoms as well as diatomic molecules are reviewed. Finally, a summary and outlook is given.atomic calculations, density functional theory, diatomic calculations, fully numerical electronic structure theory, Hartree-Fock | INTRODUCTIONThanks to decades of development in approximate density functionals and numerical algorithms, density functional theory [1,2] (DFT) is now one of the cornerstones of computational chemistry and solid-state physics. [3][4][5] Since atoms are the basic building block of molecules, a number of popular density functionals [6][7][8][9][10] have been parametrized using ab initio data on noble gas atoms; these functionals have been used in turn as the starting point for the development of other functionals. A comparison of the results of density-functional calculations to accurate ab initio data on atoms has, however, recently sparked controversy on the accuracy of a number of recently published, commonly used density functionals. [11][12][13][14][15][16][17][18][19][20][21] This underlines that there is still room for improvement in DFT even for the relatively simple case of atomic studies.The development and characterization of new density functionals require the ability to perform accurate atomic calculations. Because atoms are the simplest chemical systems, atomic calculations may seem simple; however, they are in fact sometimes surprisingly challenging. For instance, a long-standing discrepancy between the theoretical and experimental electron affinity and ionization potential of gold has been resolved only very recently with high-level ab initio calculations. [22] Atomic calculations can also be used to formulate efficient starting guesses for molecular electronic structure calculations via either the atomic density [23,24] or the atomic potential as discussed in Ref. [25].

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Gaussian basis sets for use in correlated molecular calculations. XI. Pseudopotential-based and all-electron relativistic basis sets for alkali metal (K–Fr) and alkaline earth (Ca–Ra) elements

Cited by 183 publications

References 74 publications

A new generation of effective core potentials from correlated calculations: 4s and 4p main group elements and first row additions

A new generation of effective core potentials from correlated calculations: 4s and 4p main group elements and first row additions

Midbond basis functions for weakly bound complexes

A review on non‐relativistic, fully numerical electronic structure calculations on atoms and diatomic molecules

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