Journal article
Correlation consistent basis sets for actinides. II. The atoms Ac and Np-Lr
The Journal of chemical physics, Vol.147(8), pp.084108-084108
08/28/2017
Handle:
https://hdl.handle.net/2376/112158
PMID: 28863538
Abstract
New correlation consistent basis sets optimized using the all-electron third-order Douglas-Kroll-Hess (DKH3) scalar relativistic Hamiltonian are reported for the actinide elements Ac and Np through Lr. These complete the series of sets reported previously for Th-U [K. A. Peterson, J. Chem. Phys. 142, 074105 (2015); M. Vasiliu et al., J. Phys. Chem. A 119, 11422 (2015)]. The new sets range in size from double- to quadruple-zeta and encompass both those optimized for valence (6s6p5f7s6d) and outer-core electron correlations (valence + 5s5p5d). The final sets have been contracted for both the DKH3 and eXact 2-component (X2C) Hamiltonians, yielding cc-pVnZ-DK3/cc-pVnZ-X2C sets for valence correlation and cc-pwCVnZ-DK3/cc-pwCVnZ-X2C sets for outer-core correlation (n = D, T, Q in each case). In order to test the effectiveness of the new basis sets, both atomic and molecular benchmark calculations have been carried out. In the first case, the first three atomic ionization potentials (IPs) of all the actinide elements Ac-Lr have been calculated using the Feller-Peterson-Dixon (FPD) composite approach, primarily with the multireference configuration interaction (MRCI) method. Excellent convergence towards the respective complete basis set (CBS) limits is achieved with the new sets, leading to good agreement with experiment, where these exist, after accurately accounting for spin-orbit effects using the 4-component Dirac-Hartree-Fock method. For a molecular test, the IP and atomization energy (AE) of PuO
have been calculated also using the FPD method but using a coupled cluster approach with spin-orbit coupling accounted for using the 4-component MRCI. The present calculations yield an IP
for PuO
of 159.8 kcal/mol, which is in excellent agreement with the experimental electron transfer bracketing value of 162 ± 3 kcal/mol. Likewise, the calculated 0 K AE of 305.6 kcal/mol is in very good agreement with the currently accepted experimental value of 303.1 ± 5 kcal/mol. The ground state of PuO
is predicted to be the Σ0g+5 state.
Metrics
26 Record Views
Details
- Title
- Correlation consistent basis sets for actinides. II. The atoms Ac and Np-Lr
- Creators
- Rulin Feng - Department of Chemistry, Washington State University, Pullman, Washington 99164-4630, USAKirk A Peterson - Department of Chemistry, Washington State University, Pullman, Washington 99164-4630, USA
- Publication Details
- The Journal of chemical physics, Vol.147(8), pp.084108-084108
- Academic Unit
- Chemistry, Department of
- Publisher
- United States
- Identifiers
- 99900547719001842
- Language
- English
- Resource Type
- Journal article