论文标题

无轨道密度功能理论的替代推导

An alternative derivation of orbital-free density functional theory

论文作者

Thompson, Russell B.

论文摘要

聚合物自洽场理论技术用于在不使用密度功能理论的定理的情况下得出量子密度的功能理论。取而代之的是,从直接从哈密顿量构建的分区函数中获得了自由能,从而使结果原则上有效在有限温度下有效。发现主要的管理方程是一组修改的扩散方程,一组自一致的方程与环聚合物系统的基本相同。这些方程被证明等同于Kohn-Sham密度功能理论,并在适当的条件下降低到经典密度功能理论。从原则上讲,获得的非相互作用的动能功能是准确的,但在交换 - 相关近似的其他其他情况下,保利排除原理的通常无轨道近似。使用聚合物自洽场理论的光谱方法求解方程,该方法允许对修改的扩散方程组的集合进行评估,以与求解单个扩散方程相同的计算成本进行评估。选择一个简单的交换相关函数,以及基于壳结构的Pauli电位,以比较几个孤立的原子系统的集合平均电子密度与已知文献结果。该协议非常好,证明了替代形式主义和数值方法。考虑到与温度相关的扩散方程中的时间样参数提供了一些猜测,因为它具有尺寸的显着性,因此将类似点状的量子粒子呈现为非本地量子,类似聚合物的螺纹,在较高的尺寸热空间中。从这种角度来看,对双关闭实验的考虑可以提供等同于哥本哈根解释的结果。

Polymer self-consistent field theory techniques are used to derive quantum density functional theory without the use of the theorems of density functional theory. Instead, a free energy is obtained from a partition function that is constructed directly from a Hamiltonian, so that the results are, in principle, valid at finite temperatures. The main governing equations are found to be a set of modified diffusion equations, and the set of self-consistent equations are essentially identical to those of a ring polymer system. The equations are shown to be equivalent to Kohn-Sham density functional theory, and to reduce to classical density functional theory, each under appropriate conditions. The obtained non-interacting kinetic energy functional is, in principle, exact, but suffers from the usual orbital-free approximation of the Pauli exclusion principle in additional to the exchange-correlation approximation. The equations are solved using the spectral method of polymer self-consistent field theory, which allows the set of modified diffusion equations to be evaluated for the same computational cost as solving a single diffusion equation. A simple exchange-correlation functional is chosen, together with a shell-structure-based Pauli potential, in order to compare the ensemble average electron densities of several isolated atom systems to known literature results. The agreement is excellent, justifying the alternative formalism and numerical method. Some speculation is provided on considering the time-like parameter in the diffusion equations, which is related to temperature, as having dimensional significance, and thus picturing point-like quantum particles instead as non-local, polymer-like, threads in a higher dimensional thermal-space. A consideration of the double-slit experiment from this point of view is speculated to provide results equivalent to the Copenhagen interpretation.

扫码加入交流群

加入微信交流群

微信交流群二维码

扫码加入学术交流群,获取更多资源