Ab initio investigation of the ground and excited states of ZrO+ and NbO+. (November 2020)

• Record Type: Journal Article
• Authors: Ariyarathna, Isuru R.; Miliordos, Evangelos
• Is Part Of: Journal of quantitative spectroscopy & radiative transfer. Volume 255(2020)
• Publication Date: 2020-11
• Subjects: Ab initio calculations -- Potential energy curves -- Multi-reference configuration interaction -- valence-bond-Lewis diagrams -- Spectroscopic parameters; Spectrum analysis -- Periodicals; Radiation -- Periodicals; Analyse spectrale -- Périodiques; Rayonnement -- Périodiques; Radiation; Spectrum analysis; Periodicals; 543.0858
• DOI: 10.1016/j.jqsrt.2020.107265
• Languages: English
• ISSNs: 0022-4073

Abstract

Highlights: We used high-level ab initio quantum calculations to study low-lying electronic states of ZrO+ and NbO+. We report electronic configurations, bond distances, potential energy curves, spectroscopic constants, spin–orbit splittings, and excitation energies of low-lying electronic states of ZrO+ and NbO+. Low-lying electronic states of ZrO+ and NbO+ possess M3+O2− oxo character. We rectify spectroscopic assignments made for ZrO+ and NbO+ in the literature. Abstract: High-level ab initio quantum calculations were performed to study thirteen and sixteen low-lying electronic states of ZrO + and NbO + . We report their potential energy curves, electronic configurations, bond distances, harmonic vibrational frequencies, anharmonicities, spin–orbit splittings, and excitation energies. Chemical bonding patterns for low-lying electronic states are also proposed. The removal of one electron from the ~5sZr of ZrO creates the first three states of ZrO + (X 2 Δ, 1 2 Σ +, 1 2 Π). These three states bear oxo (Zr 3+ O 2− ) character and the remaining states show oxyl (Zr 2+ O · − ) nature. Similarly, the detachment of one electron from ~5sNb of nine low-lying states of NbO generate the nine lowest energy states of NbO + that possess oxo (Nb 3+ O 2− ) character. Low-lying electronic states of ZrO + and NbO + are very similar to their isovalent TiO + and VO + partners. The current study rectifies spectroscopic assignments made for ZrO + and NbO + in the literature.