Coordination corrected ab initio formation enthalpies

Abstract

The correct calculation of formation enthalpy is one of the enablers of ab-initio computational materials design. For several classes of systems (e.g. oxides) standard density functional theory produces incorrect values. Here we propose the "Coordination Corrected Enthalpies" method (CCE), based on the number of nearest neighbor cation-anion bonds, and also capable of correcting relative stability of polymorphs. CCE uses calculations employing the Perdew, Burke and Ernzerhof (PBE), Local Density Approximation (LDA) and Strongly Constrained and Appropriately Normed (SCAN) exchange correlation functionals, in conjunction with a quasiharmonic Debye model to treat zero-point vibrational and thermal effects. The benchmark, performed on binary and ternary oxides (halides), shows very accurate room temperature results for all functionals, with the smallest mean absolute error of 27 (24) meV/atom obtained with SCAN. The zero-point vibrational and thermal contributions to the formation enthalpies are small and with different signs -largely cancelling each other.

Co and Pt Dual‐Single‐Atoms with Oxygen‐Coordinated Co–O–Pt Dimer Sites for Ultrahigh Photocatalytic Hydrogen Evolution Efficiency

“…3) In theoretical electrochemical studies, some bisite volcano-type kinetic models of catalysts were proposed to design novel catalysts. [38][39][40][41][42] In this regard, supporting and collecting data from direct experiments are necessary in the future to further accelerate this field.…”

A Framework for Quantifying Uncertainty in DFT Energy Corrections

“…For example, our fitted corrections for N do a poor job of describing the formation enthalpy of azides. More sophisticated schemes such as the "Coordination-Corrected Formation Enthalpy" (CCE) method of Friedrich et al [16] are able to treat polyanions and elements with multiple oxidation states more accurately than the scheme presented here, albeit at the expense of a more complicated set of fitting requirements. We also note that our scheme is limited by the amount and quality of experimental formation energy data for ternary compounds.…”

“…Although DFT itself is an exact theory for computing ground-state energies, approximate DFT functionals such as the popular Perdew-Burke-Ernzerhof (PBE) functional [10] result in systematic errors, especially for diatomic gases [11,12] and transition metal compounds with localized electronic states [12][13][14]. As a result, DFT-computed formation enthalpies for compounds involving these elements can exhibit errors of several hundred meV/atom [14][15][16][17]. Errors in solid-phase reaction enthalpies that do not directly involve elements are typically smaller due to cancellation of errors, but may still differ from experimental values by tens of meV/atom [18].…”

“…The Fitted Elemental Reference Energies (FERE) method [22,23] used a single U value for all transition metals, and assigned an energy correction to every element. Other correction schemes incorporated information about the local bonding environment, such as the sulfide/disulfide corrections described by Yu et al [20], or more general correction schemes described by Aykol and Wolverton [24] and the recent "Coordination-Corrected Formation Enthalpy" (CCE) method of Friedrich et al [16].…”

“…By fitting energy corrections to experimental data, such empirical DFT correction schemes can reduce the mean absolute errors (MAEs) in computed formation enthalpies to 50 meV/atom or less [16,19,23,24], with the schemes that incorporate information about the local environment generally resulting in the smallest errors. However, the fitted corrections introduce uncertainty due to 1) uncertainty in the underlying experimental data and 2) the sensitivity of the corrections to the amount of data available for fitting.…”