Dynamics and kinetics of the reaction OH + H<sub>2</sub>S → H<sub>2</sub>O + SH on an accurate potential energy surface

Ping, Lanlan; Zhu, Yongfa; Li, Anyang; Song, Hongwei; Li, Yong; Yang, Minghui

doi:10.1039/c8cp05276j

Cited by 30 publications

(22 citation statements)

References 51 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The results obtained from analysis of the emission spectra, such as the fraction of energy released to water vibrations and the distribution of this energy between the stretching and bending modes, help to understand reaction mechanisms and dynamics. The data from analysis of the emission spectra are more and more frequently used for comparison with results of kinetics calculations 5–8 and quasi‐classical trajectory (QCT) calculations 9–13 based on high‐level computations of potential‐energy surfaces. This use, plus the availability of reliable transition‐state structures for the title reactions, encouraged us to reexamine the spectra from these reactions and obtain the best possible information from the chemiluminescence spectra.…”

Section: Introductionmentioning

confidence: 99%

Reactions of OH and OD radicals with simple thiols and sulfides studied by infrared chemiluminescence of isotopic water products: Reaction OH + CH₃SH revisited

Butkovskaya

Setser

2021

Int J of Chemical Kinetics

View full text Add to dashboard Cite

Vibrational excitation of the H2O, HOD, and D2O product molecules from the reactions of OH and OD radicals with CH3SH, CH3C(O)SH, (CH3)3CSH, H2S, and CH3SCH3 was determined by modeling the infrared emission spectra using a renovated and extended set of model spectroscopic bands. Using the deuterated reactant, CH3SD, it was possible to separate spectra of abstraction from C‐ and S‐sites, which allowed measurement of branching fractions and kinetic isotope effects for individual channels. For the OH + CH3SH reaction, branching fractions of 0.13 ± 0.03 (C─H) and 0.87 ± 0.03 (S─H) were obtained. The vibrational energy released to water from abstraction of H‐atoms from the C─H and S─H sites of the reactant molecules is described. The results reported in this paper take precedence over an earlier study of CH3SH. The vibrational energy partitioning between the stretch and bend modes of water molecules from the reactions of the thiols and related reactions of H2S and CH3SCH3 are discussed. The mechanism for the OH + CH3SSCH3 reaction was confirmed to be addition followed mainly by decomposition to CH3SH and CH3SO.

show abstract

Section: Introductionmentioning

confidence: 99%

Reactions of OH and OD radicals with simple thiols and sulfides studied by infrared chemiluminescence of isotopic water products: Reaction OH + CH₃SH revisited

Butkovskaya

Setser

2021

Int J of Chemical Kinetics

View full text Add to dashboard Cite

show abstract

“…Actually, the chosen geometry under such a condition resembles most the equilibrium geometry, guaranteeing, at least to some extent, the validity of the harmonic approximation. The new scheme has been proved to work well in many reactions. − …”

Section: Theorymentioning

confidence: 99%

Final-State-Resolved Dynamics of the H₃⁺ + CO → H₂ +HCO⁺/HOC⁺ Reaction: A Quasi-Classical Trajectory Study

et al. 2020

Self Cite

View full text Add to dashboard Cite

The ion–molecule reaction H3 + + CO → H2 + HCO+/HOC+, which initiates the formation of crucial organic molecules, plays a key role in interstellar and circumstellar environments. In this work, the quasi-classical trajectory method is employed to study the reaction dynamics on a recently developed full-dimensional global potential energy surface (PES). The calculated product internal energy distributions and relative internal excited fractions agree reasonably well with the experimental measurements. For the two reaction channels, most of the available energy flows into the vibrational modes of HCO+ or HOC+ at low collision energies, followed by the translational mode and the rotational modes of HCO+ or HOC+. As the collision energy increases, the proportion of the product translational energy increases while the proportion of the product vibrational energy decreases. Furthermore, the CH and CO stretching modes and their combination bands are effectively excited for the product HCO+ while the bending mode is remarkably excited for the product HOC+.

show abstract

“…The vibrational state of the product DF is computed by the Einstein–Brillouin–Keller semiclassical quantization of the action integral . The vibrational state distribution of ND 2 is calculated by the normal mode analysis (NMA) method. − The coordinates and momenta used in NMA calculations are extracted from a specific step of each trajectory, which is determined on the condition that the corresponding geometry has the lowest potential energy within the last several vibrational periods of ND 2 , minimizing the effect of the harmonic approximation. − Two binning methods, namely, histogram binning (HB) and energy-based Gaussian binning (1GB), ,, are utilized to assign the product quantum state. The zero-point energy (ZPE) leakage is an intrinsic defect in classical trajectory simulations.…”

Section: Theorymentioning

confidence: 99%

Kinetic and Dynamic Studies of the F(²P) + ND₃ → DF + ND₂ Reaction

et al. 2021

Self Cite

View full text Add to dashboard Cite

The fast F reaction with NH3 poses a big challenge to experimental studies because of secondary chemical and collisional reactions. The quasi-classical trajectory method is utilized to investigate the mode specificity, product energy disposal, and temperature dependence of the thermal rate coefficient of F + ND3 → DF + ND2 on a recently developed potential energy surface. The effect of isotopic substitution is explored by comparing the F + ND3 reaction with the F + NH3 reaction. The computed results permit a better understanding of the F + ammonia reaction. The DF vibrational state has a Λ-type distribution, in accordance with the experimental measurement by the fast flow reactor technique. The product ND2 is dominantly populated in the ground state, and a considerable amount of ND2 is produced in the fundamental states of the bending mode. The similar vibrational state distributions of HF and NH2 in the F + NH3 reaction indicate a weak isotopic substitution effect on the product energy disposal. Exciting the umbrella mode of ND3 suppresses the reaction at low energies below 5 kcal mol–1, in sharp contrast to the observation in the F + NH3 reaction. These dynamical behaviors can be partially explained by the sudden vector projection model. In addition, the thermal rate coefficient of F + ND3 shows no temperature dependence in the range between 150 and 2000 K. There exists an inverse kinetic isotope effect at temperatures from 150 to 1500 K.

show abstract

Dynamics and kinetics of the reaction OH + H₂S → H₂O + SH on an accurate potential energy surface

Abstract: Mode specificity and product energy disposal are unveiled in the reaction OH + H2S → H2O + SH.

Cited by 30 publications

References 51 publications

Reactions of OH and OD radicals with simple thiols and sulfides studied by infrared chemiluminescence of isotopic water products: Reaction OH + CH₃SH revisited

Reactions of OH and OD radicals with simple thiols and sulfides studied by infrared chemiluminescence of isotopic water products: Reaction OH + CH₃SH revisited

Final-State-Resolved Dynamics of the H₃⁺ + CO → H₂ +HCO⁺/HOC⁺ Reaction: A Quasi-Classical Trajectory Study

Kinetic and Dynamic Studies of the F(²P) + ND₃ → DF + ND₂ Reaction

Contact Info

Product

Resources

About

Dynamics and kinetics of the reaction OH + H2S → H2O + SH on an accurate potential energy surface

Abstract: Mode specificity and product energy disposal are unveiled in the reaction OH + H2S → H2O + SH.

Cited by 30 publications

References 51 publications

Reactions of OH and OD radicals with simple thiols and sulfides studied by infrared chemiluminescence of isotopic water products: Reaction OH + CH3SH revisited

Reactions of OH and OD radicals with simple thiols and sulfides studied by infrared chemiluminescence of isotopic water products: Reaction OH + CH3SH revisited

Final-State-Resolved Dynamics of the H3+ + CO → H2 +HCO+/HOC+ Reaction: A Quasi-Classical Trajectory Study

Kinetic and Dynamic Studies of the F(2P) + ND3 → DF + ND2 Reaction

Contact Info

Product

Resources

About

Dynamics and kinetics of the reaction OH + H₂S → H₂O + SH on an accurate potential energy surface

Reactions of OH and OD radicals with simple thiols and sulfides studied by infrared chemiluminescence of isotopic water products: Reaction OH + CH₃SH revisited

Reactions of OH and OD radicals with simple thiols and sulfides studied by infrared chemiluminescence of isotopic water products: Reaction OH + CH₃SH revisited

Final-State-Resolved Dynamics of the H₃⁺ + CO → H₂ +HCO⁺/HOC⁺ Reaction: A Quasi-Classical Trajectory Study

Kinetic and Dynamic Studies of the F(²P) + ND₃ → DF + ND₂ Reaction