Article
Mass-independent Dunham analysis of the known electronic states of platinum sulfide, PtS, and analysis of the electronic field-shift effect
The Journal of Chemical Physics
(2019)
Abstract
Several new vibrational bands of the [12.5] Ω = 0+–X3Σ−Ω=0+ and the [15.9] B Ω = 0+–X3Σ−Ω=0+ transitions have been observed in high resolution absorption measurements recorded using Intracavity Laser Spectroscopy (ILS). These new bands have been rotationally analyzed and incorporated into a comprehensive PtS dataset that was fit to a mass-independent Dunham expression using PGOPHER. The comprehensive dataset included all reported field-free, gas phase spectroscopic data for PtS, including 32 Fourier transform microwave transitions (estimated accuracy: 1 kHz), 9 microwave/optical double resonance transitions (25 kHz), 51 millimeter and submillimeter transitions (25–50 kHz), 469 molecular beam-laser induced fluorescence transitions (0.003 cm−1), and 4870 ILS transitions (0.005 cm−1). The determined equilibrium constants have been used with the Rydberg-Klein-Rees method to produce potential energy curves for the four known electronic states of PtS. Isotopic shifts in electronic transition energy beyond expectations from the Born-Oppenheimer approximation were observed and treated as electronic field-shift effects due to the difference in the nuclear charge radius between Pt isotopes. The magnitude and sign of the determined field-shift parameters are rationalized through the analysis of the previously reported ab initio calculations.
Keywords
- Potential energy surfaces,
- Properties of nuclei,
- Gas phase,
- Born-Oppenheimer approximation,
- Laser spectroscopy,
- Isotopic shift
Disciplines
Publication Date
2019
DOI
https://doi.org/10.1063/1.5113510
Publisher Statement
This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in [Harms, J.C., O’Brien, L.C., and O’Brien, J.J. (2019). Mass-independent Dunham analysis of the known electronic states of platinum sulfide, PtS, and analysis of the electronic field-shift effect. The Journal of Chemical Physics 151, 094303.] and may be found at https://doi.org/10.1063/1.5113510.
Citation Information
Jack C. Harms, Leah C. O'Brien and James O'Brien. "Mass-independent Dunham analysis of the known electronic states of platinum sulfide, PtS, and analysis of the electronic field-shift effect" The Journal of Chemical Physics Vol. 51 Iss. 9 (2019) Available at: http://works.bepress.com/james-obrien/26/