Spin-Orbit Coupling Constants in Atoms and Ions of Transition Elements: Comparison of Effective Core Potentials, Model Core Potentials, and All-Electron Methods

Shiro Koseki; Nikita Matsunaga; Toshio Asada; Michael W Schmidt; Mark S Gordon

doi:10.1021/acs.jpca.8b09218

Spin-Orbit Coupling Constants in Atoms and Ions of Transition Elements: Comparison of Effective Core Potentials, Model Core Potentials, and All-Electron Methods

J Phys Chem A. 2019 Mar 28;123(12):2325-2339. doi: 10.1021/acs.jpca.8b09218. Epub 2019 Mar 12.

Authors

Shiro Koseki^{1

2}, Nikita Matsunaga³, Toshio Asada^{1

2}, Michael W Schmidt⁴, Mark S Gordon⁴

Affiliations

¹ Department of Chemistry, Graduate School of Science, Osaka Prefecture University , 1-1 Gakuen-cho , Sakai , Osaka 599-8531 , Japan.
² The Research Institute for Molecular Electronic Devices (RIMED) , Osaka Prefecture University , 1-1 Gakuen-cho , Naka-ku, Sakai 599-8531 , Japan.
³ Department of Chemistry & Biochemistry , Long Island University , Brooklyn , New York 11201 , United States.
⁴ Department of Chemistry , Iowa State University and Ames Laboratory-USDOE , Ames , Iowa 50011 , United States.

PMID: 30817150
DOI: 10.1021/acs.jpca.8b09218

Abstract

The spin-orbit coupling constants (SOCC) in atoms and ions of the first- through third-row transition elements were calculated for the low-lying atomic states whose main electron configuration is [ nd] ^q ( q = 1-4 and 6-9, n = the principal quantum number), using four different approaches: (1) a nonrelativistic Hamiltonian used to construct multiconfiguration self-consistent field (MCSCF) wave functions utilizing effective core potentials and their associated basis sets within the framework of second-order configuration interaction (SOCI) to calculate spin-orbit couplings (SOC) using one-electron Breit-Pauli Hamiltonian (BPH), (2) a nonrelativistic Hamiltonian used to construct MCSCF wave functions utilizing model core potentials and their associated basis sets within the framework of SOCI to calculate SOC using the full BPH, (3) nonrelativistic and spin-independent relativistic Hamiltonians used to construct MCSCF wave functions utilizing all-electron (AE) basis sets within the framework of SOCI to calculate SOC using the full BPH, and (4) a relativistic Hamiltonian given by the exact two-component (X2C) transformation for construction of Kramers-restricted relativistic configuration interaction wave functions. In this investigation, these four approaches are referred to as ECP, MCP, AE, and X2C methods, respectively. The ECP, MCP, and AE methods are so-called two-step approaches (TSA), while the X2C method is a one-step approach (OSA). In the AE method, three different calculations-relativistic elimination of small components (RESC), third-order Douglas-Kroll-Hess (DKH3), and infinite-order two-component (IOTC) relativistic correction-were performed for the estimation of the scalar relativistic components in addition to those of the nonscalar relativistic (NSR) contributions. The calculated SOCC are compared to the available experimental data via the Landé interval rule. Although there are several exceptions, including states whose main configuration is [ nd]⁵, the average differences between the ECP and AE (IOTC) SOCC and between the ECP and the X2C SOCC are mostly less than 20%. The differences between the ECP and the experimental SOCC are even smaller. No serious discrepancy was found between the TSA and OSA predictions of SOCC for the first- and second-row transition elements in comparison to experiment. For atoms and ions of the third-row transition elements, the SOCC calculated through the Landé interval rule are not reliable. The low-energy spin-mixed (SM) states originating from a [5d] ^q configuration ( q = 2-4) have a larger energy lowering due to the SOC effects, in comparison with those for atoms and ions of the first- and second-row transition elements. For the spin-mixed (SM) states originating from a [5d] ^q configuration ( q = 6-8), the energy lowering of all ⁴F_7/2, ⁵D₁, and ⁵D₃ states due to the SOC effects is smaller than those of the other SM states. This difficulty, which also arises for the MCP, AE, and X2C (OSA) approaches, suggests that the LS-coupling scheme is inappropriate.