Infrared spectra and structures of isotopically enriched sulfur (S3 and S4) in solid argon

Brabson, G. Dana; Mielke, Zofia; Andrews, Lester

doi:10.1021/j100154a019

Cited by 94 publications

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“…[14] The 34 S counterparts were observed at 666.4, 663.3, and 660.7 cm -1 , which define 32:34 isotopic frequency ratios (1.0306, 1.0305, and 1.0304) in agreement with those observed for the argon matrix isolated species. In the mixed 32 S and 34 S isotopic experiments a doublet of these matrix site split triplets was observed without any intermediate mixed isotopic components, which indicates that S 3 is probably produced here by photodissociation of the S 8 precursor molecules with UV radiation from the intense laser ablation plume on the surface of the uranium target.…”

Section: Ussupporting

confidence: 68%

Matrix Infrared Spectroscopy and a Theoretical Investigation of SUO and US₂

et al. 2011

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US2 and SUO molecules have been prepared by laser ablation of the solid materials and reaction of the elements during condensation in solid argon, which give the same absorptions as earlier U atom reactions with sulfur vapor and sulfur dioxide. The antisymmetric stretching mode of US2 shifts from 438.7 cm–1 in solid argon to 442.3 cm–1 in solid neon, which shows that the same electronic state is trapped in both matrix environments. Density functional calculations find a bent (3B2) ground state for the US2 molecule, and CASSCF/CASPT2 calculations reveal a multiconfigurational mixture of (5fφ)1(5fδ)1‐type states, whereas the most stable state for UO2 is a linear structure of the (5fφ)(7s) type. The bent triplet ground state SUO molecule exhibits similar multireference character with the U–O stretching mode at 857.1 cm–1 in solid argon. The linear SUO molecule computed at the CASPT2 level is only 2 kcal/mol above the bent structure. A detailed analysis of the bonding in US2 and SUO is provided and compared to the better known UO2 molecule.

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Section: Ussupporting

confidence: 68%

Matrix Infrared Spectroscopy and a Theoretical Investigation of SUO and US₂

et al. 2011

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“…The higher resolution of SEVI compared to conventional PES should facilitate vibrational assignments, but Figure 1 shows that similar problems regarding vibrational temperature remain for S 3 − . The top trace in Figure 1 was acquired using the same pulsed, free-jet source with a ring ionizer for S 3 − before the installation of the ion trap. This spectrum is dominated by the ν 1 progression and shows additional smaller peaks between the main features.…”

Section: ■ Discussionmentioning

confidence: 99%

“…Its relatively small size makes it accessible to experiment and theory, and additional interest comes about because S 3 is isovalent with ozone. It has been studied by rare gas matrix IR and UV−vis spectroscopy, 3,4 resonance Raman in the gas phase, 5,6 microwave spectroscopy, 7,8 photoionization, 9 and gas-phase absorption. 10 Ab initio calculations on S 3 have focused on the question of whether the cyclic D 3h or the bent C 2v structure is the lowestenergy isomer, 11−14 finding overall agreement with experiment that the C 2v form is the stable form.…”

Section: ■ Introductionmentioning

confidence: 99%

Slow photoelectron velocity-map imaging spectroscopy of cold negative ions

Hock

Kim

Weichman

et al. 2012

The Journal of Chemical Physics

116

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We report high-resolution anion photoelectron spectra of thiozonide (S 3 − ) acquired by slow electron velocity-map imaging (SEVI). The ions were cryogenically cooled within an ion trap before photodetachment. We measure an electron affinity of 2.3630(9) eV, resolving discrepancies in previously reported photoelectron spectra that resulted from the presence of vibrational hot bands. The SEVI spectrum shows well-resolved, extended vibrational progressions in the symmetric stretch and bending modes of S 3 , yielding accurate frequencies for both. ■ INTRODUCTIONWith the possible exception of carbon, sulfur has more complex allotropy than any other element. 1 In addition to the numerous cyclic and polymeric forms in the solid and liquid phases, sulfur vapor is composed of the species S n (2 ≤ n ≤ 8), with trace amounts of S 9 and S 10 . 2 Aside from the diatomic S 2 , S 3 has received the most attention of these species. Its relatively small size makes it accessible to experiment and theory, and additional interest comes about because S 3 is isovalent with ozone. It has been studied by rare gas matrix IR and UV−vis spectroscopy, 3,4 resonance Raman in the gas phase, 5,6 microwave spectroscopy, 7,8 photoionization, 9 and gas-phase absorption. 10 Ab initio calculations on S 3 have focused on the question of whether the cyclic D 3h or the bent C 2v structure is the lowestenergy isomer, 11−14 finding overall agreement with experiment that the C 2v form is the stable form. High-level calculations on the structure, vibrations, and excited states of S 3 have recently been reported by Francisco et al. 15,16 In contrast to neutral S 3 , work on the S 3 − anion has largely been limited to spectroscopy in condensed phases, where it has been studied by electron paramagnetic resonance (EPR), Raman, and absorption spectroscopy. 17−19 As it is the chromophore in ultramarine pigment, 20 many of these investigations were focused on determining the properties of S 3 − in a perturbative mineral matrix or in solution. In addition, electronic absorption spectra have been measured in a cryogenic rare gas matrix. 21 Recently, the anion has been identified as the dominant form of sulfur in certain highpressure and temperature conditions approximating crustal and subduction-zone geologic fluids. 22 The new findings suggest that S 3 − may play an important role in the transport of sulfur and chalcophile metals in the earth.The neutral ← anion transition has been studied by anion photoelectron spectroscopy (PES) with resolution sufficient to resolve a progression of the ν 1 symmetric stretch. 23−25 However, the two previous studies disagreed over which peak in this progression was the vibrational origin. By assuming the anions were at the ground vibrational state, Nimlos et al. 23 obtained an electron affinity (EA) of 2.106(23) eV. Hunsicker et al. 24 found a different onset for the band, suggesting the possibility that the two experiments produced anions with different vibrational temperatures and that some of the low binding en...

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“…A direct test of the thermal polymerization of small sulfur allotropes was performed by Brabson et al (1991). In their study, Brabson et al (1991) applied a microwave discharge in sulfur vapor and condensed the obtained gas at 12 K. Using infrared spectroscopy coupled with isotopic shift analysis they convincingly concluded that the samples produced are mainly composed of S 2 , S 3 , and S 4 , with less abundance of higher sulfur chains. Annealing these samples results in a decrease of allotrope bands and an increase in bands assigned to larger cyclic sulfur molecules.…”

Section: Introductionmentioning

confidence: 99%

Production of Sulfur Allotropes in Electron Irradiated Jupiter Trojans Ice Analogs

Mahjoub

Poston

Blacksberg

et al. 2017

ApJ

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In this paper, we investigate sulfur chemistry in laboratory analogs of Jupiter Trojans and Kuiper Belt Objects (KBOs). Electron irradiation experiments of CH 3 OH-NH 3 -H 2 O and H 2 S-CH 3 OH-NH 3 -H 2 O ices were conducted to better understand the chemical differences between primordial planetesimals inside and outside the sublimation line of H 2 S. The main goal of this work is to test the chemical plausibility of the hypothesis correlating the color bimodality in Jupiter Trojans with sulfur chemistry in the incipient solar system. Temperature programmed desorption (TPD) of the irradiated mixtures allows the detection of small sulfur allotropes (S 3 and S 4 ) after the irradiation of H 2 S containing ice mixtures. These small, red polymers are metastable and could polymerize further under thermal processing and irradiation, producing larger sulfur polymers (mainly S 8 ) that are spectroscopically neutral at wavelengths above 500 nm. This transformation may affect the spectral reflectance of Jupiter Trojans in a different way compared to KBOs, thereby providing a useful framework for possibly differentiating and determining the formation and history of small bodies. Along with allotropes, we report the production of organosulfur molecules. Sulfur molecules produced in our experiment have been recently detected by Rosetta in the coma of 67P/Churyumov-Gerasimenko. The very weak absorption of sulfur polymers in the infrared range hampers their identification on Trojans and KBOs, but these allotropes strongly absorb light at UV and Visible wavelengths. This suggests that high signal-to-noise ratio UV-Vis spectra of these objects could provide new constraints on their presence.

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Infrared spectra and structures of isotopically enriched sulfur (S3 and S4) in solid argon

Cited by 94 publications

References 0 publications

Matrix Infrared Spectroscopy and a Theoretical Investigation of SUO and US₂

Matrix Infrared Spectroscopy and a Theoretical Investigation of SUO and US₂

Slow photoelectron velocity-map imaging spectroscopy of cold negative ions

Production of Sulfur Allotropes in Electron Irradiated Jupiter Trojans Ice Analogs

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Infrared spectra and structures of isotopically enriched sulfur (S3 and S4) in solid argon

Cited by 94 publications

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Matrix Infrared Spectroscopy and a Theoretical Investigation of SUO and US2

Matrix Infrared Spectroscopy and a Theoretical Investigation of SUO and US2

Slow photoelectron velocity-map imaging spectroscopy of cold negative ions

Production of Sulfur Allotropes in Electron Irradiated Jupiter Trojans Ice Analogs

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Product

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Matrix Infrared Spectroscopy and a Theoretical Investigation of SUO and US₂

Matrix Infrared Spectroscopy and a Theoretical Investigation of SUO and US₂