Investigation of the Abstraction and Dissociation Mechanism in the Nitrogen Trifluoride Channels: Combined Post-Hartree–Fock and Transition State Theory Approaches

Claudino, Daniel; Gargano, Ricardo; Carvalho-Silva, Valter H.; Silva, Geraldo Magela e; Cunha, Wiliam Ferreira da

doi:10.1021/acs.jpca.6b04947

Cited by 10 publications

(5 citation statements)

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“…This formulation uniformly covers the range from classical to moderate tunneling regimes but is inadequate for deep tunneling. The proposed variant of transition-state theory permits comparison with experiments and tests against alternative formulations (see e.g., Claudino et al, 2016; Santin et al, 2016; Sanches-Neto et al, 2017).…”

Section: Beyond Eyringmentioning

confidence: 99%

“…We also generalize the sub -Arrhenius case discussing in a uniform way the trend toward Wigner' limit (Wigner, 1948), yielding Nakamura-Takayanagi-Sato (NTS) formula (Nakamura et al, 1989) and Aquilanti-Sanches-Coutinho-Carvalho (ASCC) (Coutinho et al, 2018b) at low temperature. In section Transition-State Theory Extended to Moderate Tunneling ( d -TST), the sub -Arrhenius case appropriate for extending the Transition-State Theory of Eyring (the d -TST formalism) is accounted for, as introduced and applied recently (Claudino et al, 2016; Carvalho-Silva et al, 2017; Sanches-Neto et al, 2017). A special attention will be devoted in section Viscosity and Diffusion From the Transitivity Function to a derivation of the temperature dependence of viscosity of fluids from the transitivity function γ according for the super -Arrhenius behavior and establishing the connection with the diffusion coefficient through the Stokes-Einstein equation.…”

Section: Introductionmentioning

confidence: 99%

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Temperature Dependence of Rate Processes Beyond Arrhenius and Eyring: Activation and Transitivity

2019

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Advances in the understanding of the dependence of reaction rates from temperature, as motivated from progress in experiments and theoretical tools (e. g., molecular dynamics), are needed for the modeling of extreme environmental conditions (e.g., in astrochemistry and in the chemistry of plasmas). While investigating statistical mechanics perspectives (Aquilanti et al., 2017b , 2018 ), the concept of transitivity was introduced as a measure for the propensity for a reaction to occur. The Transitivity plot is here defined as the reciprocal of the apparent activation energy vs. reciprocal absolute temperature. Since the transitivity function regulates transit in physicochemical transformations, not necessarily involving reference to transition-state hypothesis of Eyring, an extended version is here proposed to cope with general types of transformations. The transitivity plot permits a representation where deviations from Arrhenius behavior are given a geometrical meaning and make explicit a positive or negative linear dependence of transitivity for sub - and super -Arrhenius cases, respectively. To first-order in reciprocal temperature, the transitivity function models deviations from linearity in Arrhenius plots as originally proposed by Aquilanti and Mundim: when deviations are increasingly larger, other phenomenological formulas, such as Vogel-Fulcher-Tammann, Nakamura-Takayanagi-Sato, and Aquilanti-Sanches-Coutinho-Carvalho are here rediscussed from the transitivity concept perspective and with in a general context. Emphasized is the interest of introducing into this context modifications to a very successful tool of theoretical kinetics, Eyring's Transition-State Theory: considering the behavior of the transitivity function at low temperatures, in order to describe deviation from Arrhenius behavior under the quantum tunneling regime, a “ d -TST” formulation was previously introduced (Carvalho-Silva et al., 2017 ). In this paper, a special attention is dedicated to a derivation of the temperature dependence of viscosity, making explicit reference to feature of the transitivity function, which in this case generally exhibits a super -Arrhenius behavior. This is of relevance also for advantages of using the transitivity function for diffusion-controlled phenomena.

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Section: Beyond Eyringmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Temperature Dependence of Rate Processes Beyond Arrhenius and Eyring: Activation and Transitivity

2019

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“…Temperature ranges for the validity of the approach are assessed with respect to features of the potential energy barrier to reaction [20,112], permitting comparison with experiments and tests against alternative formulations. Elementary reactions, widely investigated both experimentally and theoretically, which have been described successfully, are F + H 2 [28,96], F + HD [113], CH 4 + OH [20], CH 3 Cl + OH [20], H 2 + CN [20], and also abstraction and dissociation in the nitrogen trifluoride channels [114], and proton rearrangement in curcumin [115] and methylhydroxycarbene [116]. The deformed formulation has also been found useful to describe other reactions not involving tunnelling but showing non-negligible sub-Arrhenius behaviour, such as the C + CH + reaction [117], which is of relevance in cold interstellar clouds.…”

Section: (Ii) Deformed Transition-state Theorymentioning

confidence: 99%

Kinetics of low-temperature transitions and a reaction rate theory from non-equilibrium distributions

Aquilanti

Coutinho

Carvalho-Silva

2017

Phil. Trans. R. Soc. A.

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relaxing the thermodynamic equilibrium limit, either for a binomial distribution if d > 0 or for a negative binomial distribution if d < 0, formally corresponding to Fermionlike or Boson-like statistics, respectively. The current status of the phenomenology is illustrated emphasizing case studies; specifically (i) the super-Arrhenius kinetics, where transport phenomena accelerate processes as the temperature increases; (ii) the sub-Arrhenius kinetics, where quantum mechanical tunnelling propitiates low-temperature reactivity; (iii) the anti-Arrhenius kinetics, where processes with no energetic obstacles are rate-limited by molecular reorientation requirements. Particular attention is given for case (i) to the treatment of diffusion and viscosity, for case (ii) to formulation of a transition rate theory for chemical kinetics including quantum mechanical tunnelling, and for case (iii) to the stereodirectional specificity of the dynamics of reactions strongly hindered by the increase of temperature.This article is part of the themed issue 'Theoretical and computational studies of nonequilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces'.

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“…In order to include quantum tunneling effects along the reaction coordinate into our treatment, the tunneling Wigner (κ W ), Bell 1935 (κ B 0 ), and Bell 1958 (κ B 1 and κ B 2 ) tunneling correction and deformed theory ( d -TST) − are used as follows where v † is the imaginary frequency for crossing the barrier. The crossover temperature, T c = ℏ v † / k B , is the parameter that delimits the degree of tunneling regimes: negligible ( T > 4 T c ), moderate ( T c < T < 2 T c ), and deep ( T < T c ) .…”

Section: Computational Proceduresmentioning

confidence: 99%

Methanol Solvation Effect on the Proton Rearrangement of Curcumin’s Enol Forms: An Ab Initio Molecular Dynamics and Electronic Structure Viewpoint

et al. 2016

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The recognition of the solvent effect on the enol–enol tautomerism in curcumin can guide the rationalization of systems of chemical and biological interest. Although the phenomenon is widely studied, the nature of the proton rearrangement involving the explicit solvation remains an important issue. In this study, we describe the phenomenon by an ab initio approach in gas-phase and methanol solution. The mechanism involved in the proton rearrangement has been investigated by Car–Parrinello molecular dynamics and the static M062X/DFT method. The free-energy landscape and potential energy surface in the methanol environment were explored and compared with the gas-phase one. The energy profile in methanol medium shows asymmetrical proton distribution in the curcumin enol forms and, inversely, a symmetrical behavior in the gas phase. The Gilli π-delocalization index and the HOMO orbital shape show a slight decrease in the resonance-assisted hydrogen bond (RAHB) in the solvated enol forms, different from the gas-phase system. The thermal rate constant of the intramolecular proton transfer indicated that the tunneling effect plays an important role when the curcumin molecule is under the influence of methanol. These results suggest a criterion to characterize the symmetry of the potential energy profile for the intramolecular proton transfer.

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Investigation of the Abstraction and Dissociation Mechanism in the Nitrogen Trifluoride Channels: Combined Post-Hartree–Fock and Transition State Theory Approaches

Cited by 10 publications

References 57 publications

Temperature Dependence of Rate Processes Beyond Arrhenius and Eyring: Activation and Transitivity

Temperature Dependence of Rate Processes Beyond Arrhenius and Eyring: Activation and Transitivity

Kinetics of low-temperature transitions and a reaction rate theory from non-equilibrium distributions

Methanol Solvation Effect on the Proton Rearrangement of Curcumin’s Enol Forms: An Ab Initio Molecular Dynamics and Electronic Structure Viewpoint

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