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Title: Correlation consistent basis sets for actinides. II. The atoms Ac and Np–Lr

 [1]; ORCiD logo [1]
  1. Department of Chemistry, Washington State University, Pullman, Washington 99164-4630, USA
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Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 8; Related Information: CHORUS Timestamp: 2018-02-14 17:14:15; Journal ID: ISSN 0021-9606
American Institute of Physics
Country of Publication:
United States

Citation Formats

Feng, Rulin, and Peterson, Kirk A. Correlation consistent basis sets for actinides. II. The atoms Ac and Np–Lr. United States: N. p., 2017. Web. doi:10.1063/1.4994725.
Feng, Rulin, & Peterson, Kirk A. Correlation consistent basis sets for actinides. II. The atoms Ac and Np–Lr. United States. doi:10.1063/1.4994725.
Feng, Rulin, and Peterson, Kirk A. 2017. "Correlation consistent basis sets for actinides. II. The atoms Ac and Np–Lr". United States. doi:10.1063/1.4994725.
title = {Correlation consistent basis sets for actinides. II. The atoms Ac and Np–Lr},
author = {Feng, Rulin and Peterson, Kirk A.},
abstractNote = {},
doi = {10.1063/1.4994725},
journal = {Journal of Chemical Physics},
number = 8,
volume = 147,
place = {United States},
year = 2017,
month = 8

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on August 30, 2018
Publisher's Accepted Manuscript

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Cited by: 1work
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  • New correlation consistent basis sets based on both pseudopotential (PP) and all-electron Douglas-Kroll-Hess (DKH) Hamiltonians have been developed from double- to quadruple-zeta quality for the actinide atoms thorium and uranium. Sets for valence electron correlation (5f6s6p6d), cc − pV nZ − PP and cc − pV nZ − DK3, as well as outer-core correlation (valence + 5s5p5d), cc − pwCV nZ − PP and cc − pwCV nZ − DK3, are reported (n = D, T, Q). The -PP sets are constructed in conjunction with small-core, 60-electron PPs, while the -DK3 sets utilized the 3rd-order Douglas-Kroll-Hess scalar relativistic Hamiltonian. Bothmore » series of basis sets show systematic convergence towards the complete basis set limit, both at the Hartree-Fock and correlated levels of theory, making them amenable to standard basis set extrapolation techniques. To assess the utility of the new basis sets, extensive coupled cluster composite thermochemistry calculations of ThF{sub n} (n = 2 − 4), ThO{sub 2}, and UF{sub n} (n = 4 − 6) have been carried out. After accurately accounting for valence and outer-core correlation, spin-orbit coupling, and even Lamb shift effects, the final 298 K atomization enthalpies of ThF{sub 4}, ThF{sub 3}, ThF{sub 2}, and ThO{sub 2} are all within their experimental uncertainties. Bond dissociation energies of ThF{sub 4} and ThF{sub 3}, as well as UF{sub 6} and UF{sub 5}, were similarly accurate. The derived enthalpies of formation for these species also showed a very satisfactory agreement with experiment, demonstrating that the new basis sets allow for the use of accurate composite schemes just as in molecular systems composed only of lighter atoms. The differences between the PP and DK3 approaches were found to increase with the change in formal oxidation state on the actinide atom, approaching 5-6 kcal/mol for the atomization enthalpies of ThF{sub 4} and ThO{sub 2}. The DKH3 atomization energy of ThO{sub 2} was calculated to be smaller than the DKH2 value by ∼1 kcal/mol.« less
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  • Correlation consistent basis sets for accurately describing core-core and core-valence correlation effects in atoms and molecules have been developed for the second row atoms Al - Ar. Two different optimization strategies were investigated, which led to two families of core-valence basis sets when the optimized functions were added to the standard correlation consistent basis sets (cc-pVnZ). In the first case, the exponents of the augmenting primitive Gaussian functions were optimized with respect to the difference between all-electron and valence-electron correlated calculations, i.e., for the core-core plus core-valence correlation energy. This yielded the cc-pCVnZ family of basis sets, which are analogousmore » to the sets developed previously for the first row atoms[D.E. Woon and T.H. Dunning, Jr., J. Chem. Phys. 103, 4572 (1995)]. Although the cc-pCVnZ sets exhibit systematic convergence to the all-electron correlation energy at the complete basis set limit, the intershell (core-valence ) correlation energy converges more slowly than the intrashell (core-core) correlation energy. Since the effect of including the core electrons on the calculation of molecular properties tends to be dominated by core-valence correlation effects, a second scheme for determining the augmenting functions was investigated. In this approach, the exponents of the functions to be added to the cc-pVnZ sets were optimized with respect to just the core-valence (intershell) correlation energy, except that a small amount of core-core correlation energy was included in order to ensure systematic convergence to the complete basis set limit. These new sets, denoted weighted core-valence basis sets (cc-pwCVnZ), significantly improve the convergence of many molecular properties with n. Optimum cc-pwCVnZ sets for the first-row atoms were also developed and show similar advantages.« less
  • In this work, the correlation consistent family of Gaussian basis sets has been expanded to include all-electron basis sets for In–Xe. The methodology for developing these basis sets is described, and several examples of the performance and utility of the new sets have been provided. Dissociation energies and bond lengths for both homonuclear and heteronuclear diatomics demonstrate the systematic convergence behavior with respect to increasing basis set quality expected by the family of correlation consistent basis sets in describing molecular properties. Comparison with recently developed correlation consistent sets designed for use with the Douglas-Kroll Hamiltonian is provided.
  • Cited by 13