论文标题

没有电子扰动的相对能量通过炼金术积分转换

Relative energies without electronic perturbations via Alchemical Integral Transform

论文作者

Krug, Simon León, von Rudorff, Guido Falk, von Lilienfeld, O. Anatole

论文摘要

我们表明,可以从不受干扰的系统的电子密度中充分回收扰动系统的能量。我们通过以传输,链条规则和按零件进行参数化空间来得出炼金术积分转换。在收敛的半径内,零订单在所有订单上都产生能量扩展,从而限制了Wigner的教科书声明,即$ p $ -th订单波函数衍生衍生物对于描述$(2P+1)$ - th Energy衍生产品是必需的。不需要电子密度的导数,这允许仅一个量子计算而不是单个系统覆盖整个化学邻域。提供的数值证据表明,在MHA的范围内,谐波振荡器或Morse电位以及机器样原子的机器精度范围实现了预测精度。考虑一个从HE到NE的所有多电子原子中一个质子的ISO电子核电荷变化,基于炼金术积分转换的基于相对能量的估计值仅偏离相应的Hartree-fock参考数字。

We show that the energy of a perturbed system can be fully recovered from the unperturbed system's electron density. We derive an alchemical integral transform by parametrizing space in terms of transmutations, the chain rule and integration by parts. Within the radius of convergence, the zeroth order yields the energy expansion at all orders, restricting the textbook statement by Wigner that the $p$-th order wave function derivative is necessary to describe the $(2p+1)$-th energy derivative. Without the need for derivatives of the electron density, this allows to cover entire chemical neighborhoods from just one quantum calculation instead of single systems one-by-one. Numerical evidence presented indicates that predictive accuracy is achieved in the range of mHa for the harmonic oscillator or the Morse potential, and in the range of machine accuracy for hydrogen-like atoms. Considering iso-electronic nuclear charge variations by one proton in all multi-electron atoms from He to Ne, alchemical integral transform based estimates of the relative energy deviate by only few mHa from corresponding Hartree-Fock reference numbers.

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