Effect of anharmonicity on diffusion jump rates

DeLorenzi, G; Flynn, C. P.; Jacucci, Gianni

doi:10.1103/physrevb.30.5430

Cited by 21 publications

(5 citation statements)

References 11 publications

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“…Although not explicitly recognized as such, a formulation of classical TST was presented in which the transition-state dividing surface is curved. , The curved dividing surface goes through the saddle point and is tangent to the conventional TST dividing surface at the saddle point. It is defined by a quadratic expansion of the dividing surface (not the potential) about the saddle point and includes anharmonic effects.…”

Section: Reactions In the Condensed Phasementioning

confidence: 99%

Current Status of Transition-State Theory

1996

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We present an overview of the current status of transition-state theory and its generalizations. We emphasize (i) recent improvements in available methodology for calculations on complex systems, including the interface with electronic structure theory, (ii) progress in the theory and application of transition-state theory to condensed-phase reactions, and (iii) insight into the relation of transition-state theory to accurate quantum dynamics and tests of its accuracy via comparisons with both experimental and other theoretical dynamical approximations.

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Section: Reactions In the Condensed Phasementioning

confidence: 99%

Current Status of Transition-State Theory

1996

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“…This means that correlations between successive hops are negligible and diffusion can be considered a stochastic process ͑i.e., Markovian͒. Such an assumption is valid for most solids 27 with the exception of those exhibiting liquidlike diffusion.…”

Section: A Diffusion Coefficientmentioning

confidence: 99%

First-principles theory of ionic diffusion with nondilute carriers

et al. 2001

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Many multicomponent materials exhibit significant configurational disorder. Diffusing ions in such materials migrate along a network of sites that have different energies and that are separated by configuration dependent activation barriers. We describe a formalism that enables a first-principles calculation of the diffusion coefficient in solids exhibiting configurational disorder. The formalism involves the implementation of a local cluster expansion to describe the configuration dependence of activation barriers. The local cluster expansion serves as a link between accurate first-principles calculations of the activation barriers and kinetic Monte Carlo simulations. By introducing a kinetically resolved activation barrier, we show that a cluster expansion for the thermodynamics of ionic disorder can be combined with a local cluster expansion to obtain the activation barrier for migration in any configuration. This ensures that in kinetic Monte Carlo simulations, detailed balance is maintained at all times and kinetic quantities can be calculated in a properly equilibrated thermodynamic state. As an example, we apply this formalism for an investigation of lithium diffusion in Li x CoO 2. A study of the activation barriers in Li x CoO x within the local density approximation shows that the migration mechanism and activation barriers depend strongly on the local lithium-vacancy arrangement around the migrating lithium ion. By parametrizing the activation barriers with a local cluster expansion and applying it in kinetic Monte Carlo simulations, we predict that lithium diffusion in layered Li x CoO 2 is mediated by divacancies at all lithium concentrations. Furthermore, due to a strong concentration dependence of the activation barrier, the predicted diffusion coefficient varies by several orders of magnitude with lithium concentration x.

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“…3a) were firstly compared. 25–28 Among the various alloy materials, it was found that In shows the lowest Li + migration energy barrier (∼0.16 eV) (Fig. 3b and S4†), indicating that the Li + is capable of transporting through an In interphase with low overpotential.…”

Section: Selecting In As An Interphase For Li/namentioning

confidence: 99%