Virial relations in density embedding
Virial relations in density embedding
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DOI：
10.1002/qua.26204
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发表时间：
2020-03-05
影响因子：
2.2
通讯作者：
Wasserman, Adam
中科院分区：
文献类型：
--
作者：
Jiang, Kaili;Mosquera, Martin A.;Wasserman, Adam
通过各种密度嵌入技术计算的电荷转移激发能、溶剂致变色位移和其他环境效应的准确性主要取决于非加性非相互作用动能泛函T-s(nad)[n]所采用的近似值。逼近这种泛函仍然是电子结构理论中的一个重要挑战。为了帮助开发和测试T-s(nad)[n]的近似，我们推导了分子中片段的两个维里关系。这些建立了非相互作用和相互作用电子系统的非加性动能之间的独立联系，以及诸如电子-核力，分配（或嵌入）能量和势以及系统及其部分的Kohn-Sham势等数量。我们在双原子分子上数值验证了这两种关系。
The accuracy of charge-transfer excitation energies, solvatochromic shifts, and other environmental effects calculated via various density-embedding techniques depend critically on the approximations employed for the nonadditive noninteracting kinetic energy functional, T-s(nad)[n]. Approximating this functional remains an important challenge in electronic-structure theory. To assist in the development and testing of approximations for T-s(nad)[n], we derive two virial relations for fragments in molecules. These establish separate connections between the nonadditive kinetic energies of the noninteracting and interacting systems of electrons, and quantities such as the electron-nuclear attraction forces, the partition (or embedding) energy and potential, and the Kohn-Sham potentials of the system and its parts. We numerically verify both relations on diatomic molecules.