Characterizing electronic states and spectra in transition metal-rare gas diatomic cations: The cases of VAr+ and VKr+. (January 2022)

• Record Type: Journal Article
• Authors: Romeu, João Gabriel Farias; de Melo, Gabriel Fernando; Ornellas, Fernando R.
• Is Part Of: Journal of quantitative spectroscopy & radiative transfer. Volume 277(2022)
• Publication Date: 2022-01
• Subjects: Transition metal-rare gas cations -- Potential energy curves -- Spectroscopic parameters -- Transition moments -- Transition probabilities for emission -- Absorption spectra; Spectrum analysis -- Periodicals; Radiation -- Periodicals; Analyse spectrale -- Périodiques; Rayonnement -- Périodiques; Radiation; Spectrum analysis; Periodicals; 543.0858
• DOI: 10.1016/j.jqsrt.2021.107959
• Languages: English
• ISSNs: 0022-4073

Abstract

Highlights: Reliable potential energy curves for the quintet electronic states of VAr + and VKr + . Most complete characterization of these cations states to date. Dipole and transition moments, einstein Av´v´´ emission coefficients, and radiative lifetimes. Absorption spectra for the g 5 Π – X 5 Σ + band systems modelled with intensity peaks clearly identified. Abstract: Nine low-lying quintet electronic states of the cations VAr + and VKr + are characterized theoretically at the SA-CASSCF/icMRCI/aug-cc-pV5Z level of theory by the construction of potential energy curves and the determination of spectroscopic parameters. The polarity of the molecules is described by dipole moment functions and vibrationally averaged dipole moments. Transition probabilities for spontaneous emission for selected states are estimated by the Einstein Av´, v´´ coefficients and the stronger transitions identified; radiative lifetimes are also reported. For the photoabsorption process, the spectrum is modelled for the bands of the G 5 Π – X 5 Σ + system of each species for which experimental photodissociation results are available in the literature. Not known experimentally, the intensity distribution is expected to help elucidate the assumed vibrational numbering of the upper state, and together with the overall electronic description and spectroscopic parameters motivate further experimental investigations of transition metal-rare-gas cations. Binding arises from purely electrostatic charge-induced dipole interaction. Graphical abstract: Image, graphical abstract