Alchemical derivatives of reaction energetics.
Alchemical derivatives of reaction energetics.
复制标题
反应能量学的炼金术导数。
DOI：
10.1063/1.3474502
复制
发表时间：
2010
期刊：
影响因子：
--
通讯作者：
O. A. von Lilienfeld
中科院分区：
文献类型：
--
作者：
D. Sheppard;G. Henkelman;O. A. von Lilienfeld
基于分子巨正则系综密度泛函理论，我们从理论上描述了当系统中的原子从一种元素转变为另一种元素时，反应势垒和焓是如何变化的。氨伞式转化的能势势的变化是沿着分子转化为水的炼金术路径计算的，甲烷的质子化焓的变化是通过氨、水和氟化氢将分子转化为氖原子计算的。从无扰动系统中的静电势解析计算了炼金术导数，并与用被变换原子的伪势的有限差分插值计算的数值导数进行了比较。在解析导数和数值导数之间发现了很好的一致性。炼金术衍生物还被证明可以预测氧与79个原子的钯纳米粒子结合时原子序数的整数变化，说明它们在基于梯度的优化算法中用于合理设计催化剂的潜在用途。
Based on molecular grand canonical ensemble density functional theory, we present a theoretical description of how reaction barriers and enthalpies change as atoms in the system are subjected to alchemical transformations, from one element into another. The change in the energy barrier for the umbrella inversion of ammonia is calculated along an alchemical path in which the molecule is transformed into water, and the change in the enthalpy of protonation for methane is calculated as the molecule is transformed into a neon atom via ammonia, water, and hydrogen fluoride. Alchemical derivatives are calculated analytically from the electrostatic potential in the unperturbed system, and compared to numerical derivatives calculated with finite difference interpolation of the pseudopotentials for the atoms being transformed. Good agreement is found between the analytical and numerical derivatives. Alchemical derivatives are also shown to be predictive for integer changes in atomic numbers for oxygen binding to a 79 atom palladium nanoparticle, illustrating their potential use in gradient-based optimization algorithms for the rational design of catalysts.