Observation of the 5p Rydberg states of sulfur difluoride radical by resonance-enhanced multiphoton ionization spectroscopy

TL;DR

This study identifies three new Rydberg states of sulfur difluoride radical using resonance-enhanced multiphoton ionization spectroscopy, advancing understanding of its electronic structure and photodissociation behavior.

Contribution

The paper reports the first observation and characterization of three previously unknown Rydberg states of sulfur difluoride radical via REMPI spectroscopy.

Findings

Identification of three new Rydberg states labeled K, L, and M.

Determination of vibrational frequencies and energy levels of these states.

Discussion of the photofragmentation process related to the observed spectra.

Abstract

Sulfur difluoride radicals in their ground state have been produced by a "laser-free" pulsed dc discharge of the SF$_{6}$/Ar gas mixtures in a supersonic molecular beam and detected by mass-selective resonance-enhanced multilphoton ionization (REMPI) spectroscopy in the wavelength range of 408 - 420 nm. Analyses of the (3 + 1) REMPI excitation spectrum have enabled identification of three hitherto unknown Rydberg states of this radical. Following the Rydberg state labeling in our previous work [see J. Phys. Chem. A 102, 7233 (1998)], these we label the K(5p$_{1}$) [$nu_{0-0}$ = 71 837 cm$^{-1}$, $omega_{1}^{'}$(a$_{1}$ sym str) = 915 cm$^{-1}$], L(5p$_{2}$) [$nu_{0-0}$ = 72 134 cm$^{-1}$, $omega_{1}^{'}$(a$_{1}$ sym str) = 912 cm$^{-1}$], and M(5p$_{3}$) [$nu_{0-0}$ = 72 336 cm$^{-1}$, $omega_{1}^{'}$(a$_{1}$ sym str) = 926 cm$^{-1}$] Rydberg states, respectively. [Origins, relative to the lowest vibrational level of the X$^{1}$A$_{1}$ ground state, and vibrational frequencies of the symmetric S-F stretching mode are suggested by the numbers in brackets.] Photofragmentation process of SF$_{2}$$^{+}$--SF$^{+}$ + F that relates to the REMPI spectrum was discussed.