Mass-independent Dunham analysis of the known electronic states of platinum sulfide, PtS, and analysis of the electronic field-shift effect

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.

A wafer-scale two-dimensional platinum monosulfide ultrathin film via metal sulfurization for high performance photoelectronics

“…10–12 Platinum sulfide has shown extraordinary mechanical, 13,14 optical, electronic, magnetic 15 and phase transition properties. 16 A few reports on 2D PtS exist including electronic structure calculations, 17,18 spectral analysis 19 and nonlinear optical device applications. 20 Besides, 2D PtS has been recently integrated into van der Waals heterostructures 21 for enhancing the device performances.…”

Exciton‐Like and Mid‐Gap Absorption Dynamics of PtS in Resonant and Transparent Regions

“…[7] Unexpected electronic field shift was recently noted by Harms et al when they employed a high resolution intracavity laser spectroscopy. [8] Although efforts and progress on comprehending the properties of PtS have been ongoing, they thus far mainly concentrated upon the structure and synthesis, [5][6][7][9][10][11] the electrical properties, [11][12][13][14][15] and a few on the optical properties including our latest work on optical nonlinearity and ultrafast optics aspects from the bulk to their 2D form. [16][17][18][19] The global optical property of PtS, however, is still suffering a significant knowledge gap.…”