论文标题

在有限温度下,金属卤化物钙钛矿的准确有效的带隙预测

Accurate and efficient band-gap predictions for metal halide perovskites at finite temperature

论文作者

Wang, Haiyuan, Tal, Alexey, Bischoff, Thomas, Gono, Patrick, Pasquarello, Alfredo

论文摘要

我们开发一种计算有效的方案,以准确确定有限的温度带隙。我们在这里关注属于ABX3类的材料(a = rb,cs; b = ge,sn,pb; and x = f,cl,br,i),其中包括卤化物perovskites。首先,通过使用范围分离的杂交功能,为理想的晶体结构提供了带隙的初始估计值,其中参数是从电子密度和高频介电常数中非经验确定的。接下来,我们考虑两种带隙校正,以说明旋转轨道耦合和热振动,包括零点运动。特别是,后一种效应是通过特殊位移方法来解释的,该方法包括使用从振动频率和特征码中获得的单个变形构型,从而避免了冗长的分子动力学。对两种校正的顺序考虑都会系统地改善频带差距,相对于实验值,达到0.17 eV的平均绝对误差。我们方案的计算效率源于以下事实:在混合功能水平上仅进行单个计算,并且足以评估半局部理论水平的校正。对于大型系统和筛选大型材料数据库,我们的方案特别方便。

We develop a computationally efficient scheme to accurately determine finite-temperature band gaps. We here focus on materials belonging to the class ABX3 (A = Rb, Cs; B = Ge, Sn, Pb; and X = F, Cl, Br, I), which includes halide perovskites. First, an initial estimate of the band gap is provided for the ideal crystalline structure through the use of a range-separated hybrid functional, in which the parameters are determined nonempirically from the electron density and the high-frequency dielectric constant. Next, we consider two kinds of band-gap corrections to account for spin-orbit coupling and thermal vibrations including zero-point motions. In particular, the latter effect is accounted for through the special displacement method, which consists in using a single distorted configuration obtained from the vibrational frequencies and eigenmodes, thereby avoiding lengthy molecular dynamics. The sequential consideration of both corrections systematically improves the band gaps, reaching a mean absolute error of 0.17 eV with respect to experimental values. The computational efficiency of our scheme stems from the fact that only a single calculation at the hybrid-functional level is required and that it is sufficient to evaluate the corrections at the semilocal level of theory. Our scheme is particularly convenient for large-size systems and for the screening of large databases of materials.

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