Kinetic and dynamic studies of the H3+ + CO → H2 + HCO+/HOC+ reaction on a high-level <i>ab initio</i> potential energy surface

Zhu, Yongfa; Tian, Li; Song, Hongwei; Yang, Minghui

doi:10.1063/1.5110934

Cited by 19 publications

(26 citation statements)

References 61 publications

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“…In X – + CH 3 Y (X, Y = F, Cl, Br, I, OH, etc.) reactions, for example, the competition of the S N 2 (CH 3 X + Y – ) and the PT (HX + CH 2 Y – ) channels has been a recent topic of dynamic investigations. ,,, Similarly, product branching in neutral reactions has also attracted much current attention. ,,,− These dynamical studies were mostly made possible by global multichannel PESs.…”

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confidence: 99%

Advances and New Challenges to Bimolecular Reaction Dynamics Theory

Zhao

Xie

et al. 2020

J. Phys. Chem. Lett.

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Dynamics of bimolecular reactions in the gas phase are of foundational importance in combustion, atmospheric chemistry, interstellar chemistry, and plasma chemistry. These collision-induced chemical transformations are a sensitive probe of the underlying potential energy surface(s). Despite tremendous progress in past decades, our understanding is still not complete. In this Perspective, we survey the recent advances in theoretical characterization of bimolecular reaction dynamics, stimulated by new experimental observations, and identify key new challenges.

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confidence: 99%

Advances and New Challenges to Bimolecular Reaction Dynamics Theory

Zhao

Xie

et al. 2020

J. Phys. Chem. Lett.

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“…or quantum dynamical (QD) calculations, a reliable full-dimensional potential energy surface (PES) is required. 31 Thanks to advances in various neural network (NN)-based fitting methods, [32][33][34][35] reliable full-dimensional PESs for reactive systems with up to seven atoms [36][37][38][39][40][41][42][43][44][45][46][47][48] are reported by fitting hundreds of thousands of configurations, whose energies were determined at the explicitly correlated CCSD(T) with the AVTZ basis set (CCSD(T)-F12a/AVTZ). 49,50 However, due to the long-range interactions between the negatively charged ions and the neutral molecules, 2 the PES of R1 covers a huge configuration space, particularly in the reactant or product channels, making the construction of the full-dimensional accurate PES more challenging.…”

Section: Introductionmentioning

confidence: 99%

Validating Experiments for the Reaction H2 + NH2- by Dynamical Calculations on an Accurate Full-Dimensional Potential Energy Surface

Song

2022

Preprint

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Ion-molecule reactions play key roles in the field of ion related chemistry. As a prototypical multi-channel ion-molecule reaction, the reaction H2 + NH2- → NH3 + H- has been studied for decades. In this work, we develop a globally accurate potential energy surface (PES) for the title system based on hundreds of thousands of sampled points over a wide dynamically relevant region that covers long-range interacting configuration space. The permutational invariant polynomial-neural network (PIP-NN) method is used for fitting and the resulting total root mean squared error (RMSE) is extremely small, 0.026 kcal mol-1. Extensive dynamical and kinetic calculations are carried out on this new PIP-NN PES by the quasi-classical trajectory (QCT) method. The calculated rate coefficients for H2 / D2 + NH2- agree well with the experimental results, which show an inverse temperature dependence from 50 to 300 K, consistent with the capture nature of this barrierless reaction. The significant kinetic isotope effect observed by experiment is well reproduced by the QCT computations as well. In addition, we report a unique phenomenon of significant reactivity suppression by exciting the rotational mode of H2, supported by both QCT and quantum dynamics (QD) calculations. Further analysis uncovers that exciting the H2 rotational mode would prevent the formation of the reactant complex and thus suppress reactivity.

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“…Thus, theoretical prediction of various physical quantities is essential. Several theoretical studies have been performed. − For example, Le et al constructed a full-dimensional potential energy surface using an interpolation technique and performed quasi-classical trajectory (QCT) calculations . Zhu et al.…”

Section: Introductionmentioning

confidence: 99%

Ring-Polymer Molecular Dynamics Calculations of Thermal Rate Coefficients and Branching Ratios for the Interstellar H₃⁺ + CO → H₂ + HCO⁺/HOC⁺ Reaction and Its Deuterated Analogue

2021

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The reaction between H3 + and CO is important in understanding the H3 + destruction mechanism in the interstellar medium. In this work, thermal rate coefficients for the H3 + + CO and D3 + + CO reactions are calculated using ring-polymer molecular dynamics (RPMD) on a high-level machine-learning potential energy surface. The RPMD results agree well with the classical molecular dynamics results, where nuclear quantum effects are completely ignored, whereas the agreement between the RPMD results and the previous quasi-classical trajectory is good only at low temperatures. The calculated [HCO+]/[HOC+] product branching ratios decrease as the temperature increases, and the product branching is exclusively determined by the initial collisional orientation, which governs the formation of an ion–dipole complex, H3 +···CO or H3 +···OC, that dissociates into H2 + HCO+ or H2 + HOC+, respectively, via a direct mechanism. However, the contribution of the indirect mechanism via the rearrangement between H3 +···CO and H3 +···OC increases as the temperature increases, although its absolute fraction is small.

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Kinetic and dynamic studies of the H3+ + CO → H2 + HCO+/HOC+ reaction on a high-level ab initio potential energy surface

Cited by 19 publications

References 61 publications

Advances and New Challenges to Bimolecular Reaction Dynamics Theory

Advances and New Challenges to Bimolecular Reaction Dynamics Theory

Validating Experiments for the Reaction H2 + NH2- by Dynamical Calculations on an Accurate Full-Dimensional Potential Energy Surface

Ring-Polymer Molecular Dynamics Calculations of Thermal Rate Coefficients and Branching Ratios for the Interstellar H₃⁺ + CO → H₂ + HCO⁺/HOC⁺ Reaction and Its Deuterated Analogue

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Kinetic and dynamic studies of the H3+ + CO → H2 + HCO+/HOC+ reaction on a high-level ab initio potential energy surface

Cited by 19 publications

References 61 publications

Advances and New Challenges to Bimolecular Reaction Dynamics Theory

Advances and New Challenges to Bimolecular Reaction Dynamics Theory

Validating Experiments for the Reaction H2 + NH2- by Dynamical Calculations on an Accurate Full-Dimensional Potential Energy Surface

Ring-Polymer Molecular Dynamics Calculations of Thermal Rate Coefficients and Branching Ratios for the Interstellar H3+ + CO → H2 + HCO+/HOC+ Reaction and Its Deuterated Analogue

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Ring-Polymer Molecular Dynamics Calculations of Thermal Rate Coefficients and Branching Ratios for the Interstellar H₃⁺ + CO → H₂ + HCO⁺/HOC⁺ Reaction and Its Deuterated Analogue