Quenching processes in electronically excited sulfur dioxide generated by chemical reaction

Glinski, Robert J.; Dixon, David A.

doi:10.1021/j100406a009

Cited by 7 publications

(3 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“… a Reference . b T 0 , refs − . c r 0 , ref . d Reference . e Reference . T e , T v , and singlet–triplet gap ( E S – E T ) are in units of kcal/mol.…”

Section: Resultsmentioning

confidence: 99%

Theoretical Studies of the Excited Doublet States of SF and SCl and Singlet States of SF₂, SFCl, and SCl₂

Leiding

Dunning

2012

J. Phys. Chem. A

View full text Add to dashboard Cite

In previous work, we reported that the lowest-lying excited states of SF, SCl, SF(2), SFCl, and SCl(2) have recoupled pair bonds. In this study, we examine the analogous low-spin states--the (2)Σ(-) and (2)Δ states of SF and SCl and the excited singlet states of SF(2), SCl(2), and SFCl--which also possess recoupled pair bonds. In contrast to the excited states treated previously, the states studied in the present work have the same spin multiplicities as their respective ground states and are thus potentially observable via electronic excitation. Of particular interest are the minima on the (1)A″ potential energy surface of SFCl corresponding to bond-stretch isomers analogous to those found on the (3)A″ surface. In addition, we discovered that the first two excited states ((1)A″) accessible via vertical excitations from the ground state of SFCl have the electronic structure of the bond-stretch isomers. Thus, electronic excitation spectroscopic studies of SFCl could reveal a signature of the bond-stretch isomers. We will also present limited data on the lowest singlet Rydberg states of the triatomic species. Calculations were performed at the MRCI+Q/aug-cc-pV(Q+d,5+d)Z levels of theory.

show abstract

“… a Reference . b T 0 , refs − . c r 0 , ref . d Reference . e Reference . T e , T v , and singlet–triplet gap ( E S – E T ) are in units of kcal/mol.…”

Section: Resultsmentioning

confidence: 99%

Theoretical Studies of the Excited Doublet States of SF and SCl and Singlet States of SF₂, SFCl, and SCl₂

Leiding

Dunning

2012

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…CH2=SF'CH3. The first AIE and VIE of this molecule at the RHF/6-31 G*//RHF/6-31G* level were computed as 6.88 and 7.77 eV, respectively. As expected, these values increase when electron correlation is included in the calculations, to 8.17 and 8.94 eV at the RMP2/6-31 G*//RMP2/6-31G* level.…”

Section: Computational Detailsmentioning

confidence: 99%

A Study of the Reactions of Molecular Fluorine with CH3SCH3 and CH3SSCH3 with UV Photoelectron Spectroscopy: First Observation of the HFCS Molecule

Baker¹,

Butcher²,

Dyke³

et al. 1995

J. Phys. Chem.

View full text Add to dashboard Cite

The title reactions have been investigated in the gas phase using UV photoelectron spectroscopy. By recording spectra at different reaction times, it was possible to detect reaction intermediates and hence identify pathways by which each reaction proceeds. The F2 + CH3SCH3 reaction appears to proceed via the intermediate CH3-SFCH3 whereas the F2 + CH3SSCH3 reaction gives H2CS and HF as the first observed products. For both reactions at longer reaction times, a new spectrum associated with a reaction product, consisting of three photoelectron bands with adiabatic ionization energies of 10.15 f 0.01, 11.49 f 0.02, and 13.71 0.01 eV, has been observed. This spectrum is assigned to the HFCS molecule. The first two adiabatic ionization energies of HFCS have been calculated using the Gaussian-2 (G2) theoretical procedure as 10.09 and 1 1.5 1 eV, respectively, supporting this assignment. This work represents the first observation and spectroscopic study of this molecule. A broad band with a vertical ionization energy of 10.58 f 0.06 eV, assigned to the first ionization energy of HCF, has also been observed as a secondary product from both reactions under conditions of excess F2 partial pressure. This assignment is supported by first adiabatic and vertical ionization energies of HCF computed at the G2 level of theory. For each reaction, a reaction mechanism is proposed on the basis of the results obtained.

show abstract

“…Since that early work, three electronically excited states ( ã 3 B 1 , Ã 1 A 2 , and B̃ 1 B 1 ) of SO 2 have been relatively well characterized. , The Ã and B̃ states both contribute to a broad fluorescence continuum in the wavelength range 280−380 nm with markedly different lifetimes and quenching rate constants. Glinski et al have shown that the phosphorescent state ( ã 3 B 1 ), which provides a highly characteristic banded emission in the wavelength range 380−460 nm, is not produced directly in the chemiluminescent reaction but is formed through collisionally induced intersystem crossing from one of the singlet states. , Both Benner 1 and Martin and Glinski found that the emission spectrum of SO 2 * obtained in the reaction of the effluent of a SO 2 -doped, hydrogen-rich flame with ozone matched extremely well the emission spectrum produced in the reaction of SO with ozone, where SO was produced by fragmentation of SO 2 in a microwave discharge.…”

mentioning

confidence: 96%

Flow Tube Kinetics Investigation of the Mechanism of Detection in the Sulfur Chemiluminescence Detector

Burrow

Birks

1997

Anal. Chem.

View full text Add to dashboard Cite

Rate constants and their temperature dependencies were measured for the chemiluminescent reaction of ozone with the flame and furnace effluents of two commercially available sulfur detectors, the Sulfur Chemiluminescence detector (registered trademark of Sievers Instruments, Inc.) and the Chemiluminescent Sulfur Detector (registered trademark of Antek Instruments, Inc.). The absolute rate constants and activation energies agreed within experimental error with the well-established values for the SO + O(3) reaction in all detector configurations. When ozone was present in the reaction zone, the reaction of the furnace effluent with NO(2) also was in good agreement with the rate constant for the SO + NO(2) reaction. However, when ozone was not present in the reaction zone, little or no reaction occurred with NO(2). These results imply that an unknown sulfur species, X, is formed in the combustion zone and/or transfer line of the instrument and converted to SO upon reaction with ozone in the chemiluminescence detection cell. Based on our experimental results and known reaction rate constants, we can eliminate S(2), S(2)O, SO(2), S(2)O(2), HS, HSO, HSO(2), HOSO(2), and H(2)S as X. We hypothesize that X is S(3) formed in the association reaction of S atoms with S(2) within the transfer line.

show abstract

Quenching processes in electronically excited sulfur dioxide generated by chemical reaction

Cited by 7 publications

References 3 publications

Theoretical Studies of the Excited Doublet States of SF and SCl and Singlet States of SF₂, SFCl, and SCl₂

Theoretical Studies of the Excited Doublet States of SF and SCl and Singlet States of SF₂, SFCl, and SCl₂

A Study of the Reactions of Molecular Fluorine with CH3SCH3 and CH3SSCH3 with UV Photoelectron Spectroscopy: First Observation of the HFCS Molecule

Flow Tube Kinetics Investigation of the Mechanism of Detection in the Sulfur Chemiluminescence Detector

Contact Info

Product

Resources

About

Quenching processes in electronically excited sulfur dioxide generated by chemical reaction

Cited by 7 publications

References 3 publications

Theoretical Studies of the Excited Doublet States of SF and SCl and Singlet States of SF2, SFCl, and SCl2

Theoretical Studies of the Excited Doublet States of SF and SCl and Singlet States of SF2, SFCl, and SCl2

A Study of the Reactions of Molecular Fluorine with CH3SCH3 and CH3SSCH3 with UV Photoelectron Spectroscopy: First Observation of the HFCS Molecule

Flow Tube Kinetics Investigation of the Mechanism of Detection in the Sulfur Chemiluminescence Detector

Contact Info

Product

Resources

About

Theoretical Studies of the Excited Doublet States of SF and SCl and Singlet States of SF₂, SFCl, and SCl₂

Theoretical Studies of the Excited Doublet States of SF and SCl and Singlet States of SF₂, SFCl, and SCl₂