UV spectra and kinetics of radicals produced in the gas phase reactions of Cl, F and OH with toluene

Markert, Frank; Pagsberg, P.

doi:10.1016/0009-2614(93)80115-6

Cited by 41 publications

(36 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…No rotational structure could be resolved due to lifetime and/or temperature-related broadening. In agreement with low-resolution studies, 56,57 the strongest vibrational excitation in D 3 , the ν 5 fundamental (C-C valence mode) at 4.177 eV, is about five times weaker than the origin band, signifying little geometry change upon electronic excitation. The strong D 4 state ( f calc = 0.35) with maximum absorption at 4.89 eV appears broad, without analyzable structure, and is probably mixed with nearby Rydberg states, whose presence was suggested by complete active space (CAS) calculations.…”

Section: Electronic Absorptions Of the Neutral Radicalssupporting

confidence: 86%

Probing different spin states in xylyl radicals and ions

Steglich

Bodi

Maier

et al. 2018

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

Resonant one-color two-photon ionization spectroscopy and mass-selected threshold photoelectron spectroscopy were applied to study the electronic doublet states of the three xylyl (methyl-benzyl) radicals above 3.9 eV as well as the singlet and triplet states of the cations up to 10.5 eV. The experiments are complemented by quantum chemical calculations and Franck-Condon simulations to characterize the transitions and to identify the origin bands, allowing a precise determination of singlet-triplet splittings in the cations. Torsional motions of the methyl group notably affect the D → D transition of m-xylyl. All other investigated transitions either lead to electronic states with very low rotational barriers or suffer from spectral broadening in excess of methyl torsional energy levels. The methyl internal rotational potential is faithfully reproduced with the most basic ab initio methods, yet hyperconjugation could not be identified as a significant force shaping them. Time-dependent density functional theory describes the excited electronic states better than wave function theory approaches, notably EOM-CCSD.

show abstract

Section: Electronic Absorptions Of the Neutral Radicalssupporting

confidence: 86%

Probing different spin states in xylyl radicals and ions

Steglich

Bodi

Maier

et al. 2018

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…[54]; (dashed line) k TOT 4 evaluated in Ref. [52]; (solid line) k TOT 4 calculated using the adjusted G2M barrier of 6.0 kcal/mol. CH 3 + C 4 H 9 → C 5 H 12 (25)…”

Section: Figurementioning

confidence: 99%

“…Several sources report the rate constant of the H atom addition to toluene at room T (298-303 K) in the range (0.4-2.0)×10 −13 cm 3 /(molecule s) [34,35,44,[50][51][52]. Our calculation at HPL conditions gives k 1 = 1.4 × 10 −13 cm 3 /(molecule s), more than 80% of which falls on H-addition at o-position.…”

Section: Molecular and Transition State Structuresmentioning

confidence: 99%

Kinetics and mechanism for the H‐for‐X exchange process in the H + C₆H₅X reactions: A computational study

Tokmakov

Lin

2001

Int J of Chemical Kinetics

View full text Add to dashboard Cite

The addition of H atoms to benzene and toluene and subsequent transformations were investigated using high level ab initio and density functional theory methods. Molecular structures and vibrational frequencies calculated at the B3LYP/6-311++G(d,p) level of theory were used in combination with adjusted G2M energetic parameters for RRKM rate constant calculations. Standard heats of formation for cyclohexadienyl and cyclohexadienyl, 6-methyl radicals calculated through isodesmic reactions amounted to 49.5 ± 2 and 42.9 ± 3 kcal/mol, respectively. Rate constants for various elementary reactions involved in the H-for-X exchange (X = D, CH 3 ) were calculated and closely correlated with the available experimental kinetic data.

show abstract

“…We report here the results of experiments to examine the effect of temperature on the kinetics of the reactions of Cl with toluene and the xylenes. There are kinetic results in the literature for these reactions at a fixed temperature close to 298 K and atmospheric pressure [17][18][19][20][21][22][23][24][25] but not over a range of temperatures. One of these reports 17 also presents a theoretical analysis of the relative stabilities of the addition complexes that might be expected to form between Cl and toluene.…”

mentioning

confidence: 99%

Temperature dependence of the reactions of Cl with toluene and the xylenes

FRAZEE

Roscoe

2019

Int J of Chemical Kinetics

View full text Add to dashboard Cite

The temperature dependence of the rate coefficients for the reactions of Cl with toluene and the xylenes was examined from 290 to 362 K. Chemical analysis was by gas chromatography. The relative rate method was used for the kinetic analysis, and the relative rate coefficients were converted to absolute values using absolute rate coefficients for the reference reactions obtained from recent critical evaluations. Most of the measurements were made at a total pressure of approximately 100 kPa in argon. There was very little temperature dependence, and variation of the total pressure and the concentration of O 2 had no effect. The values of the absolute rate coefficients were independent of the reference reaction used. The reaction of Cl with toluene was studied relative to the reactions of Cl with isobutane, ethane, propane, and n-butane. The results were virtually independent of temperature, giving a mean value of (5 ± 1) × 10 −11 cm 3 molecule -1 s −1 for the absolute rate coefficient at 95% confidence. The reactions of Cl with the xylenes were studied relative to the reactions of Cl with isobutane, ethane, and propane. The rate coefficients were independent of the xylene isomer and had a very small negative dependence on temperature. The mean value of the absolute rate coefficient at 298 K was (1.4 ± 0.3) × 10 −10 cm 3 molecule −1 s -1 at the 95% confidence level. The results are in satisfactory agreement with those in the literature, all of which were measured at fixed temperatures very close to 298 K. The kinetic results are discussed in relation to published descriptions of the dynamics of reactions of Cl and OH with organic compounds.

show abstract

UV spectra and kinetics of radicals produced in the gas phase reactions of Cl, F and OH with toluene

Cited by 41 publications

References 22 publications

Probing different spin states in xylyl radicals and ions

Probing different spin states in xylyl radicals and ions

Kinetics and mechanism for the H‐for‐X exchange process in the H + C₆H₅X reactions: A computational study

Temperature dependence of the reactions of Cl with toluene and the xylenes

Contact Info

Product

Resources

About

UV spectra and kinetics of radicals produced in the gas phase reactions of Cl, F and OH with toluene

Cited by 41 publications

References 22 publications

Probing different spin states in xylyl radicals and ions

Probing different spin states in xylyl radicals and ions

Kinetics and mechanism for the H‐for‐X exchange process in the H + C6H5X reactions: A computational study

Temperature dependence of the reactions of Cl with toluene and the xylenes

Contact Info

Product

Resources

About

Kinetics and mechanism for the H‐for‐X exchange process in the H + C₆H₅X reactions: A computational study