Dynamics of ion-molecule recombination. III. Trends in the recombination efficiency

Swamy, Kandadai N.; Hase, William L.

doi:10.1021/ja00327a001

Cited by 31 publications

(29 citation statements)

References 11 publications

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“…In the past, for ion–molecule recombination reactions, a different procedure for calculating k asso ( T ) was considered. , Following that approach, the calculated k ( E rel ) values using eq are fit into the equation with α and β being the fit parameters. Considering the Boltzmann distribution of E rel and using eq in eq , the expression of k asso ( T ) is obtained as …”

Section: Computational Proceduresmentioning

confidence: 99%

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Chemical Dynamics Simulations on Association and Ensuing Dissociation of a Benzene–Hexafluorobenzene Molecular System

et al. 2019

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Chemical dynamics simulations are performed to study the association of benzene (Bz) and hexafluorobenzene (HFB) followed by the ensuing dissociation of the Bz–HFB complex. The calculations are done for 1000, 1500, and 2000 K with an impact parameter (b) range of 0–10 Å at each temperature. Almost no complexes are observed to form at b = 8 and 10 Å. Following three different methods of calculation of the temperature-dependent association rate constant k asso(T), the values obtained are 1.67 × 10–10, 1.86 × 10–10, and 2.05 × 10–10 cm3/molecule·s with a standard deviation of approximately 0.1 × 10–10 cm3/molecule·s for T = 1500 K. Among those values of k asso(T), the middle one is obtained by considering a relative translational energy of 3RT/2 at T = 1500 K, and the same is followed to calculate k asso(T) at 1000 and 2000 K. The Arrhenius parameters, using the k asso(T) values at three temperatures, are 0.203 × 10–10 cm3/molecule·s for the pre-exponential factor and −5.79 kcal/mol for the activation energy. The absolute value of the latter is similar to the Bz + HFB association energy of 5.93 kcal/mol. The ensuing dissociation dynamics of the complex is significantly different from the unimolecular dissociation dynamics, and an exponential function fits the N(t – t 0)/N(t 0) curves comparatively well. The ensuing dissociation is also observed to be independent of time for a statistically large sample size.

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Section: Computational Proceduresmentioning

confidence: 99%

“…In the past, for ion−molecule recombination reactions, a different procedure for calculating k asso (T) was considered. 32,33 Following that approach, the calculated k(E rel ) values using eq 3 are fit into the equation…”

Section: Computational Proceduresmentioning

confidence: 99%

Chemical Dynamics Simulations on Association and Ensuing Dissociation of a Benzene–Hexafluorobenzene Molecular System

et al. 2019

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“…which is sufficiently accurate since the reaction cross section is not strongly energy dependent. 30,31 Each trajectory was analyzed, at the time its integration was terminated, to determine the products formed and their product energy partitioning from the total available energy. Rotational (E rot ) and vibrational (E vib ) energy was calculated for each product molecule.…”

Section: Methodsmentioning

confidence: 99%

“…A total of 200 trajectories were calculated. Using the reactive cross section and the relative velocity ( v rel ) of the reactants, the rate constant of the reaction ( k ) was calculated using the expression which is sufficiently accurate since the reaction cross section is not strongly energy dependent. , …”

Section: Computational Methodsmentioning

confidence: 99%

Direct Dynamics Simulations of the ³CH₂ + ³O₂ Reaction at High Temperature

2021

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Direct dynamics simulations with the M06/6-311++G(d,p) level of theory were performed to study the 3CH2 + 3O2 reaction at 1000 K temperature on the ground state singlet surface. The reaction is complex with formation of many different product channels in highly exothermic reactions. CO, CO2, H2O, OH, H2, O, H, and HCO are the products formed from the reaction. The total simulation rate constant for the reaction at 1000 K is (1.2 ± 0.3) × 10–12 cm3 molecule–1 s–1, while the simulation rate constant at 300 K is (0.96 ± 0.28) × 10–12 cm3 molecule–1 s–1. The simulated product yields show that CO is the dominant product and the CO:CO2 ratio is 5.3:1, in good comparison with the experimental ratio of 4.3:1 at 1000 K. On comparing the product yields for the 300 and 1000 K simulations, we observed that, except for CO and H2O, the yields of the other products at 1000 K are lower at 300 K, showing a negative temperature dependence.

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“…As a matter of fact, this kind of potential has been used to perform classical and quasiclassical trajectory calculations for these reactions. [20][21][22] In particular, the series Li', N a + , K f has been studied at 300 K. 22 As alkali-metal ion-water associations are reactions without a saddle point, CVTST is a particularly useful theory to be applied here. 23.24 However, up to now CVTST has only been applied to the Li+-H20 association reaction using the ab initio derived potential^.^^.^^ As far as we know, there is no previous work on variational kinetic calculations along the series of alkali-metal ions using the ab initio analytical potential surfaces.…”

Section: Introductionmentioning

confidence: 99%

Canonical variational transition-state comparative study for M⁺(= Li⁺, Na⁺and K⁺)+ H₂O →[M ·(H₂O)]⁺association reactions

Moreno¹,

Lluch²,

Bertrán³

1990

J. Chem. Soc., Faraday Trans.

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Dynamics of ion-molecule recombination. III. Trends in the recombination efficiency

Cited by 31 publications

References 11 publications

Chemical Dynamics Simulations on Association and Ensuing Dissociation of a Benzene–Hexafluorobenzene Molecular System

Chemical Dynamics Simulations on Association and Ensuing Dissociation of a Benzene–Hexafluorobenzene Molecular System

Direct Dynamics Simulations of the ³CH₂ + ³O₂ Reaction at High Temperature

Canonical variational transition-state comparative study for M⁺(= Li⁺, Na⁺and K⁺)+ H₂O →[M ·(H₂O)]⁺association reactions

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Dynamics of ion-molecule recombination. III. Trends in the recombination efficiency

Cited by 31 publications

References 11 publications

Chemical Dynamics Simulations on Association and Ensuing Dissociation of a Benzene–Hexafluorobenzene Molecular System

Chemical Dynamics Simulations on Association and Ensuing Dissociation of a Benzene–Hexafluorobenzene Molecular System

Direct Dynamics Simulations of the 3CH2 + 3O2 Reaction at High Temperature

Canonical variational transition-state comparative study for M+(= Li+, Na+and K+)+ H2O →[M ·(H2O)]+association reactions

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Product

Resources

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Direct Dynamics Simulations of the ³CH₂ + ³O₂ Reaction at High Temperature

Canonical variational transition-state comparative study for M⁺(= Li⁺, Na⁺and K⁺)+ H₂O →[M ·(H₂O)]⁺association reactions