Localized Resolution of Identity Approach to the Analytical Gradients of Random-Phase Approximation Ground-State Energy: Algorithm and Benchmarks

doi:10.1021/acs.jctc.2c00512

	Localized Resolution of Identity Approach to the Analytical Gradients of Random-Phase Approximation Ground-State Energy: Algorithm and Benchmarks
	Tahir, Muhammad N.1; Zhu, Tong 2; Shang, Honghui 3; Li, Jia 1; Blum, Volker 4; Ren, Xinguo 5,6
	2022-08-12
发表期刊	JOURNAL OF CHEMICAL THEORY AND COMPUTATION
ISSN	1549-9618
页码	15
摘要	We develop and implement a formalism which enables calculating the analytical gradients of particle-hole random-phase approximation (RPA) ground-state energy with respect to the atomic positions within the atomic orbital basis set framework. Our approach is based on a localized resolution of identity (LRI) approximation for evaluating the two-electron Coulomb integrals and their derivatives, and the density functional perturbation theory for computing the first -order derivatives of the Kohn-Sham (KS) orbitals and orbital energies. Our implementation allows one to relax molecular structures at the RPA level using both Gaussian-type orbitals (GTOs) and numerical atomic orbitals (NAOs). Benchmark calculations against previous implementations show that our approach delivers adequate numerical precision, highlighting the usefulness of LRI in the context of RPA gradient evaluations. A careful assessment of the quality of RPA geometries for small molecules reveals that post-KS RPA systematically overestimates the bond lengths. We furthermore optimized the geometries of the four low-lying water hexamers-cage, prism, cyclic, and book isomers, and determined the energy hierarchy of these four isomers using RPA. The obtained RPA energy ordering is in good agreement with that yielded by the coupled cluster method with single, double and perturbative triple excitations, despite that the dissociation energies themselves are appreciably underestimated. The underestimation of the dissociation energies by RPA is well corrected by the renormalized single excitation correction.
DOI	10.1021/acs.jctc.2c00512
收录类别	SCI
语种	英语
资助项目	National Natural Science Foundation of China[11874036] ; National Natural Science Foundation of China[11874335] ; Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program[2017BT01N111] ; Shenzhen Basic Research Project[JCYJ20200109142816479] ; Max Planck Partner Group for Advanced Electronic Structure Methods
WOS研究方向	Chemistry ; Physics
WOS类目	Chemistry, Physical ; Physics, Atomic, Molecular & Chemical
WOS记录号	WOS:000844674900001
出版者	AMER CHEMICAL SOC
引用统计	被引频次：10[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://119.78.100.204/handle/2XEOYT63/19447
专题	中国科学院计算技术研究所期刊论文_英文
通讯作者	Li, Jia; Blum, Volker; Ren, Xinguo
作者单位	1.Tsinghua Univ, Tsinghua Shenzhen Int Grad Sch, Guangdong Prov Key Lab Thermal Management Engn & M, Shenzhen 518055, Peoples R China 2.Duke Univ, Dept Chem, Durham, NC 27708 USA 3.Chinese Acad Sci, Inst Comp Technol, State Key Lab Comp Architecture, Beijing 100190, Peoples R China 4.Duke Univ, Thomas Lord Dept Chem, Dept Mech Engn & Mat Sci, Durham, NC 27708 USA 5.Chinese Acad Sci, Inst Phys, Beijing 100190, Peoples R China 6.Songshan Lake Mat Lab, Dongguan 523808, Guangdong, Peoples R China
推荐引用方式 GB/T 7714	Tahir, Muhammad N.,Zhu, Tong,Shang, Honghui,et al. Localized Resolution of Identity Approach to the Analytical Gradients of Random-Phase Approximation Ground-State Energy: Algorithm and Benchmarks[J]. JOURNAL OF CHEMICAL THEORY AND COMPUTATION,2022:15.
APA	Tahir, Muhammad N.,Zhu, Tong,Shang, Honghui,Li, Jia,Blum, Volker,&Ren, Xinguo.(2022).Localized Resolution of Identity Approach to the Analytical Gradients of Random-Phase Approximation Ground-State Energy: Algorithm and Benchmarks.JOURNAL OF CHEMICAL THEORY AND COMPUTATION,15.
MLA	Tahir, Muhammad N.,et al."Localized Resolution of Identity Approach to the Analytical Gradients of Random-Phase Approximation Ground-State Energy: Algorithm and Benchmarks".JOURNAL OF CHEMICAL THEORY AND COMPUTATION (2022):15.