The role of decomposition reactions in assessing first-principles predictions of solid stability

作     者：Christopher J.Bartel Alan W.Weimer Stephan Lany Charles B.Musgrave Aaron M.Holder 

作者机构：Department of Chemical and Biological EngineeringUniversity of ColoradoBoulderCO 80309USA National Renewable Energy LaboratoryGoldenCO 80401USA Department of ChemistryUniversity of ColoradoBoulderCO 80309USA 

出 版 物：《npj Computational Materials》 (计算材料学（英文）)

年 卷 期：2019年第5卷第1期

页      面：1120-1128页

核心收录：

学科分类：07[理学] 070202[理学-粒子物理与原子核物理] 0702[理学-物理学] 

基　　金：This work was supported by the National Science Foundation(award nos.CBET-1433521,CHE-1800592,and CBET-1806079) The authors also acknowledge partial support for this work from the U.S.Department of Energy,Office of Basic Energy Sciences(S.L.and A.M.H.,contract no.DE-AC36-08GO28308) Fuel Cell Technologies Office(A.W.W.and C.B.M,award no.DE-EE0008088) 

主　　题：stability stability solid 

摘      要：The performance of density functional theory approximations for predicting materials thermodynamics is typically assessed by comparing calculated and experimentally determined enthalpies of formation from elemental phases,ΔH_(f).However,a compound competes thermodynamically with both other compounds and their constituent elemental forms,and thus,the enthalpies of the decomposition reactions to these competing phases,ΔH_(d),determine thermodynamic *** evaluated the phase diagrams for 56,791 compounds to classify decomposition reactions into three types:*** that produce elemental phases,*** that produce compounds,and *** that produce *** analysis shows that the decomposition into elemental forms is rarely the competing reaction that determines compound stability and that approximately two-thirds of decomposition reactions involve no elemental *** experimentally reported formation enthalpies for 1012 solid compounds,we assess the accuracy of the generalized gradient approximation(GGA)(PBE)and meta-GGA(SCAN)density functionals for predicting compound *** 646 decomposition reactions that are not trivially the formation reaction,PBE(mean absolute difference between theory and experiment(MAD)=70 meV/atom)and SCAN(MAD=59 meV/atom)perform similarly,and commonly employed correction schemes using fitted elemental reference energies make only a negligible improvement(~2 meV/atom).Furthermore,for 231 reactions involving only compounds(Type 2),the agreement between SCAN,PBE,and experiment is within~35 meV/atom and is thus comparable to the magnitude of experimental uncertainty.