Localized Resolution of Identity Approach to the Analytical Gradients of Random-Phase Approximation Ground-State Energy: Algorithm and Benchmarks
文献类型：期刊论文
| 作者 | Tahir, Muhammad N.3; Zhu, Tong4; Shang, Honghui5; Li, Jia3; Blum, Volker1; Ren, Xinguo2,6 |
| 刊名 | JOURNAL OF CHEMICAL THEORY AND COMPUTATION
 |
| 出版日期 | 2022-08-12 |
| 页码 | 15 |
| ISSN号 | 1549-9618 |
| DOI | 10.1021/acs.jctc.2c00512 |
| 英文摘要 | 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. |
| 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 |
| 语种 | 英语 |
| 出版者 | AMER CHEMICAL SOC |
| WOS记录号 | WOS:000844674900001 |
| 源URL | [http://119.78.100.204/handle/2XEOYT63/19446]  |
| 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.Duke Univ, Thomas Lord Dept Chem, Dept Mech Engn & Mat Sci, Durham, NC 27708 USA 2.Songshan Lake Mat Lab, Dongguan 523808, Guangdong, Peoples R China 3.Tsinghua Univ, Tsinghua Shenzhen Int Grad Sch, Guangdong Prov Key Lab Thermal Management Engn & M, Shenzhen 518055, Peoples R China 4.Duke Univ, Dept Chem, Durham, NC 27708 USA 5.Chinese Acad Sci, Inst Comp Technol, State Key Lab Comp Architecture, Beijing 100190, Peoples R China 6.Chinese Acad Sci, Inst Phys, Beijing 100190, 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. |
入库方式： OAI收割
来源：计算技术研究所
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