Electron photodetachment of thiomethoxyl and deuterothiomethoxyl anions: Electron affinities, vibrational frequencies, and spin–orbit splitting in CH3S⋅̄ and CD3S⋅̄

Abstract

Articles you may be interested inElectronic states and spin-orbit splitting of lanthanum dimer J. Chem. Phys. 135, 034309 (2011); 10.1063/1.3615505Laser photodetachment electron spectrometry of methoxide, deuteromethoxide, and thiomethoxide: Electron affinities and vibrational structure of CH30, CD30, and CH3SThe cross section for electron photodetachment has been measured for the thiomethoxyl anion (CH)S--) and the deuterothiomethoxyl anion (CD)S -) using an ion cyclotron resonance spectrometer in conjunction with a tunable dye laser. After accounting for the effective rotational broadening, these spectra yield the electron affinities, EA(CH)S) = 1.861±0.004 eV and EA(CD)S) = 1.858±0.OO6 eV. A doubling of features is observed in the photodetachment spectra which arises from transitions to the 2E312 and 2E\12 spin--{)rbit states of the final-state radicals. From these spacings we obtain a spin--{)rbit coupling constant (A) in CH)S' of -280±50 cm-I and in CD)S' of -260±50 em-I. The spectra also contain transitions to excited vibrational states of the radicals for which we obtain vibrational frequencies of 770+ 50 cm -I for the symmetric C-S stretching motion in CH)S (660±60 em -I in CD)S) and 1360± 70 em -I fur the methyl umbrella motion (\ 100±50 cm-I in CD)S).

CAS Calculation of the Excited States of the Methylthio Neutral Radical and Its Ions

“…This value is less than 1.861 ± 0.004 eV from the photodetachment spectra experiment and a determination by the photoelectron spectrum. 22 , 23 , 36 …”

“… 21 The photodetachment experiments were also performed and yielded the C–S stretching frequency to be 680 ± 40 or 770 ± 50 in cm –1 . 22 , 23 Gillbro reported an electron spin resonance spectrum of CH 3 S produced in single crystals of CH 3 SSCH 3 from the reaction between the fluorine atom and CH 3 SH, but no definite assignment to CH 3 S was made for the observed spectra. 18 , 24 Suzuki et al.…”

Design Near-threshold Photoelectron Imaging Spectrometer Based on UV Laser Induced Photoelectron Emission Anion Source

“…excited state of CH 3 S − and S 2 − transitions at relative high temperature (∼600 K)[18]. The reported results from other groups also show significant discrepancy with each other and some results have relatively large errors.For the CH 3 S radical, the determined EA values are 1.8610±0.0040 eV[16,17], 1.882±0.022 eV[15], 1.871±0.012 eV[18], and 1.8670±0.0040 eV[19]. For the S 2 molecule, the determined EA values are: 1.565±0.050 eV[21], 1.663±0.040 eV…”

Study of the vibronic coupling in the ground state of Methylthio radical

“…It has been suggested that it may be an intermediate in the atmospheric oxidation by OH and NO3 (Mellouki et al, 1977) of organic sulfides such as CH3SCH3, CH3SSCH3 and CH3SH. It has been the subject of numerous spectroscopic studies, such as emission (Ohbayashi et al, 1977), the laser photodetachment (Janousek et al, 1980;Engelking et al, 1978), the electron paramagnetic resonance (EPR) (Gillbro , 1974), the IR matrix (Jacox , 1983), the laser-induced fluorescence (Chiang et al, 1991;Hsu et al, 1989;Suzuki et al, 1984) and the microwave (Endo et al, 1986).…”