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 canceling each other.

正确计算地层焓是从头算材料设计的促成因素之一。对于几类系统（例如氧化物），标准密度泛函理论得出的值不正确。在这里，我们基于最近邻的阳离子-阴离子键的数量，提出了“配位校正的焓”方法（CCE），并且还能够校正多晶型物的相对稳定性。CCE使用的计算方法包括Perdew，Burke和Ernzerhof（PBE），局部密度近似（LDA），强约束和适当归一化（SCAN）交换相关函数，以及准谐波Debye模型，以处理零点振动和热效应。对二元和三元氧化物（卤化物）进行的基准测试显示了所有功能的非常准确的室温结果，用SCAN获得的最小平均绝对误差为27（24）meV / atom。对地层焓的零点振动和热影响很小，并且具有不同的符号-彼此抵消。