Kinetics of Hydrogen Radical Reactions with Toluene Including Chemical Activation Theory Employing System-Specific Quantum RRK Theory Calibrated by Variational Transition State Theory

Bao, Junwei Lucas; Zheng, Jingjing; Truhlar, Donald G.

doi:10.1021/jacs.5b11938

Cited by 77 publications

(143 citation statements)

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“…On the Li metal surface with the reductive environment, the CH bond in the methyl group of toluene is first broken to yield benzyl anion and hydrogen radical. In the subsequent propagation step, the hydrogen radical formed in the initiation step attacks the toluene to produce a stable radical intermediate that can undergo resonance bond rearrangement, [18] leading to poly merization in random orientations along the benzene ring plane. In the subsequent propagation step, the hydrogen radical formed in the initiation step attacks the toluene to produce a stable radical intermediate that can undergo resonance bond rearrangement, [18] leading to poly merization in random orientations along the benzene ring plane.…”

Section: Resultsmentioning

confidence: 99%

Tuning the Electron Density of Aromatic Solvent for Stable Solid‐Electrolyte‐Interphase Layer in Carbonate‐Based Lithium Metal Batteries

Yoo

Yang

Yun

et al. 2018

Advanced Energy Materials

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green electric transportation due to its low redox potential (−3.04 V vs standard hydrogen electrode) and unprecedented theoretical capacity (3860 mAh g −1 or 2060 mAh mL −1 ). [1] In spite of these advantages, a substantial gap remains before practical application due to vulnerable dendritic growth during repeated Li deposition and stripping. Dendrite growth causes indiscriminate electrolyte decomposition and dead Li, resulting in inferior charge-discharge reversibility and ultimately severe capacity fading.Li dendrite growth has been described by two models. One is the "space charge" model. This model focuses on ion depletion at the electrode-electrolyte interface; as current density increases, an ion depletion layer on the electrode surface is formed and thickens. [2] In this interfacial evolution, Sand's time, an onset point where an ion depletion layer begins to form, serves as a useful descriptor. Above this point, due to Li ion depletion, Li ions tend to lose their homogeneous distribution in the bulk electrolyte and are rather concentrated toward local spots (so-called surface "tips") with higher electron densities. While this model well explains the behaviors of dendrite growth at different current densities, those at low current densities below Sand's time are described limitedly.The other model focuses on the "uniformity" of the solidelectrolyte-interphase (SEI) layer with respect to morphology and composition, without taking current density into consideration. [3] This model relies on a viewpoint that in the nonuniform SEI layer, Li ion transport becomes uneven over the electrode area, which accelerates dendrite growth and consequently destroys the SEI layer. Therefore, from this model's perspective, success in suppressing dendrite growth depends largely on the uniformity and durability of the SEI layer.Based on the consensus regarding the importance of a uniform SEI layer, numerous approaches have been introduced, including artificial SEI layers, [4] LiNO 3 additives, [5] vinylene carbonate additives, [6,7] fluoroethylene carbonate additives, [8] polymer electrolytes, [9] and high-concentration electrolytes (HCEs). [10][11][12][13] In the case of artificial SEI layers, while their effect is noticeable in the early cycling period, inevitable Lithium metal has been hailed as a key enabler of upcoming rechargeable batteries with high energy densities. Nonetheless, uncontrolled dendritic growth and resulting formation of a nonuniform solid-electrolyte-interphase (SEI) layer constitute an ever-challenging obstacle in long-term cyclability and safety. So far, these drawbacks have been addressed mainly by using noncarbonate electrolytes based on their relatively mild decomposition under reductive environments. Here, toluene as a co-solvent of carbonate-based electrolytes for lithium metal anodes is reported. The electron-donating nature of the methyl group of toluene shifts the reduction of toluene prior to that of commonly used carbonate solvents, resulting in a more uniform and rigid SEI layer. Moreove...

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Section: Resultsmentioning

confidence: 99%

Tuning the Electron Density of Aromatic Solvent for Stable Solid‐Electrolyte‐Interphase Layer in Carbonate‐Based Lithium Metal Batteries

Yoo

Yang

Yun

et al. 2018

Advanced Energy Materials

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“…43 The ability of the new method to incorporate variational effects in k(E) has been validated in our previous work 43 in falloff calculations with approximately the same affordable effort as is required for the canonical-ensemble high-pressure limit. 43 The ability of the new method to incorporate variational effects in k(E) has been validated in our previous work 43 in falloff calculations with approximately the same affordable effort as is required for the canonical-ensemble high-pressure limit.…”

Section: Physical Chemistry Chemical Physics Accepted Manuscriptmentioning

confidence: 95%

“…It has been described in two previous papers 43,44 but is summarized here in a form intended to make its connection to other work in the field clearer. It has been described in two previous papers 43,44 but is summarized here in a form intended to make its connection to other work in the field clearer.…”

Section: Energy-dependent Lindemann-hinshelwood Theorymentioning

confidence: 99%

“…Recently, we proposed the system-specific quantum RRK (SS-QRRK) method, 43,44 which retains the theoretical and computational simplicity of the original QRRK model, yet is able to 8 incorporate high-level electronic structure calculations into the potential energy surface and variational effects, multidimensional tunneling based on the directly calculated potential energy surface along the tunneling path, and torsional and other vibrational anharmonicity into the dynamical theory. Our SS-QRRK rate constants are calibrated by full high-pressure-limit canonical VTST direct dynamics calculations, and (aside from estimating collision rates with widely available Lennard-Jones parameters) the only empirical parameter needed for predicting falloff curves is the average energy transferred.…”

Section: Introductionmentioning

confidence: 99%

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Predicting pressure-dependent unimolecular rate constants using variational transition state theory with multidimensional tunneling combined with system-specific quantum RRK theory: a definitive test for fluoroform dissociation

Bao

Zhang

Truhlar

2016

Phys. Chem. Chem. Phys.

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108

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Understanding the falloff in rate constants of gas-phase unimolecular reaction rate constants as the pressure is lowered is a fundamental problem in chemical kinetics, with practical importance for combustion, atmospheric chemistry, and essentially all gas-phase reaction mechanisms. In the present work, we use our recently developed system-specific quantum RRK theory, calibrated by canonical variational transition state theory with small-curvature tunneling, combined with the Lindemann-Hinshelwood mechanism, to model the dissociation reaction of fluoroform (CHF3), which provides a definitive test for falloff modeling. Our predicted pressure-dependent thermal rate constants are in excellent agreement with experimental values over a wide range of pressures and temperatures. The present validation of our methodology, which is able to include variational transition state effects, multidimensional tunneling based on the directly calculated potential energy surface along the tunneling path, and torsional and other vibrational anharmonicity, together with state-of-the-art reaction-path-based direct dynamics calculations, is important because the method is less empirical than models routinely used for generating full mechanisms, while also being simpler in key respects than full master equation treatments and the full reduced falloff curve and modified strong collision methods of Troe.

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“…Then, after the calculation of the high-pressure rate constant, the pressuredependent dissociation rate constants are computed from the high-pressure rate constants using our recently proposed system-specific quantum Rice-Ramsperger-Kassel (SS-QRRK) theory with the Lindemann-Hinshelwood mechanism (30)(31)(32). SS-QRRK theory is able to effectively incorporate variational effects, anharmonicity, and multidimensional tunneling into the microcanonical rate constants needed to calculate pressure effects with negligible additional computational cost over and above the previous step of calculating high-pressure unimolecular rate constants.…”

Section: Significancementioning

confidence: 99%

Barrierless association of CF ₂ and dissociation of C ₂ F ₄ by variational transition-state theory and system-specific quantum Rice–Ramsperger–Kassel theory

Bao

Zhang

Truhlar

2016

Proc. Natl. Acad. Sci. U.S.A.

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Bond dissociation is a fundamental chemical reaction, and the first principles modeling of the kinetics of dissociation reactions with a monotonically increasing potential energy along the dissociation coordinate presents a challenge not only for modern electronic structure methods but also for kinetics theory. In this work, we use multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) to compute the highpressure limit dissociation rate constant of tetrafluoroethylene (C 2 F 4 ), in which the potential energies are computed by direct dynamics with the M08-HX exchange correlation functional. To treat the pressure dependence of the unimolecular rate constants, we use the recently developed system-specific quantum Rice-Ramsperger-Kassel theory. The calculations are carried out by direct dynamics using an exchange correlation functional validated against calculations that go beyond coupled-cluster theory with single, double, and triple excitations. Our computed dissociation rate constants agree well with the recent experimental measurements.bond dissociation | barrierless reaction | variable-reaction-coordinate variational transition-state theory | falloff | system-specific quantum RRK theory B ond breaking and association of fragments to make new bonds are two of the most fundamental processes in chemistry. Gas-phase bond dissociation and radical-radical association reactions are of great importance in combustion and plasma chemistry and atmospheric chemistry. Accurately describing the energetics and kinetics of these processes in a practical way for mechanistic analysis offers great challenges to modern theoretical chemistry.The electronic structure of closed-shell singlets can often be described to a good approximation by a single configuration state function (CSF); such systems are called single-reference systems, and methods using a single CSF as a reference function are called single-reference methods. Bond dissociation is usually an intrinsically multiconfigurational problem, often called a multireference problem (1). Coupled cluster (CC) theory (2, 3), as a high-level single-reference wave function method, is able to provide fairly accurate energies for bond-dissociation processes only if a high-enough excitation level (such as quadruple excitations) is used for the cluster operatorT; however, lack of such expensive higher excitation operators in CC calculations [such as in the case of coupled-cluster theory with single and double excitations (CCSD) (4)] can lead to a significant unphysical bump (5, 6) in the potential energy curve for dissociation. Kohn-Sham density functional theory (KS-DFT) (7,8), however, with carefully chosen exchange correlation (XC) density functionals can produce smooth potential curves for dissociation with satisfactory accuracy without introducing any unphysical bump and with much smaller computational cost; however, at this time, an XC functional that can be used as a panacea does not exist. In addition to an adequate level of electronic structure...

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Kinetics of Hydrogen Radical Reactions with Toluene Including Chemical Activation Theory Employing System-Specific Quantum RRK Theory Calibrated by Variational Transition State Theory

Cited by 77 publications

References 83 publications

Tuning the Electron Density of Aromatic Solvent for Stable Solid‐Electrolyte‐Interphase Layer in Carbonate‐Based Lithium Metal Batteries

Tuning the Electron Density of Aromatic Solvent for Stable Solid‐Electrolyte‐Interphase Layer in Carbonate‐Based Lithium Metal Batteries

Predicting pressure-dependent unimolecular rate constants using variational transition state theory with multidimensional tunneling combined with system-specific quantum RRK theory: a definitive test for fluoroform dissociation

Barrierless association of CF ₂ and dissociation of C ₂ F ₄ by variational transition-state theory and system-specific quantum Rice–Ramsperger–Kassel theory

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Kinetics of Hydrogen Radical Reactions with Toluene Including Chemical Activation Theory Employing System-Specific Quantum RRK Theory Calibrated by Variational Transition State Theory

Cited by 77 publications

References 83 publications

Tuning the Electron Density of Aromatic Solvent for Stable Solid‐Electrolyte‐Interphase Layer in Carbonate‐Based Lithium Metal Batteries

Tuning the Electron Density of Aromatic Solvent for Stable Solid‐Electrolyte‐Interphase Layer in Carbonate‐Based Lithium Metal Batteries

Predicting pressure-dependent unimolecular rate constants using variational transition state theory with multidimensional tunneling combined with system-specific quantum RRK theory: a definitive test for fluoroform dissociation

Barrierless association of CF 2 and dissociation of C 2 F 4 by variational transition-state theory and system-specific quantum Rice–Ramsperger–Kassel theory

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Barrierless association of CF ₂ and dissociation of C ₂ F ₄ by variational transition-state theory and system-specific quantum Rice–Ramsperger–Kassel theory