High-Level Coupled-Cluster Energetics by Monte Carlo Sampling and Moment Expansions

通过蒙特卡罗采样和矩展开的高级耦合团簇能量学

• 批准号: 1763371
• 负责人: Piotr Piecuch
• 金额: $ 42万
• 依托单位: Michigan State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-07-01 至 2022-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1763371&HistoricalAwards=false
• 关键词: Level; Coupled; Cluster; Energetics; Monte

Piotr Piecuch of Michigan State University is supported by an award from the Chemical Theory, Models and Computational Methods program in the Chemistry Division to develop a radically new approach to solving the many-particle Schrodinger equation. This method holds the key to explaining the motion of electrons in atoms and molecules. By understanding the details of this motion, Piecuch and his group can precisely determine the amounts of energy needed to break chemical bonds and transform reactants into products. The ability to do these calculations accurately will ultimately aid in the design of new materials, better catalysts, and more efficient energy sources. The new approach uses repeated random tests of many small energy contributions and retains those found to be most important. This approach reduces the computational costs of high-accuracy methods by orders of magnitude. Once fully developed, the methods will be shared with the community via open-source mechanisms. Findings resulting from the activities are being used in teaching courses and communicated through publications, seminars, and conference presentations. These ideas provide positive training experiences in the forefront of the physical sciences for members of the Piecuch group. This research addresses one of the key challenges in electronic structure theory, namely the development of practical and systematically improvable ab initio computational schemes aimed at an accurate description of molecular energetics. It is widely accepted that size extensive methods based on the coupled-cluster theory are excellent candidates for addressing this challenge. However, it has been notoriously difficult to incorporate higher-than two-body components of the cluster operator, needed to achieve a quantitative description, without running into prohibitive computational costs of higher-order coupled-cluster schemes. The proposed methodology solves the problem, allowing one to obtain accurate energetics equivalent to high-level coupled-cluster calculations, even when electronic quasi-degeneracies and higher-than pair excitations become significant, at a small fraction of the computational cost. It also preserves the black-box character of conventional single-reference computations, by fusing the deterministic formalism, abbreviated as CC(P;Q) with the stochastic configuration interaction and coupled-cluster Monte Carlo approaches. The formal and algorithmic advances and efficient computer implementations will be accompanied by calculations of molecular potential energy surfaces relevant to spectroscopy, chemical reaction mechanisms and dynamics, and catalysis. The work provides important training for graduate students and postdoctoral fellows and the programs being developed will be widely shared with the broader theoretical community.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

密歇根州立大学的Piotr Piecuch获得了化学系化学理论、模型和计算方法项目的奖项支持，致力于开发一种全新的方法来求解多粒子薛定谔方程。 这种方法是解释原子和分子中电子运动的关键。通过了解这种运动的细节，Piecuch和他的团队可以精确地确定打破化学键并将反应物转化为产物所需的能量。 准确地进行这些计算的能力最终将有助于设计新材料，更好的催化剂和更有效的能源。新方法使用许多小能量贡献的重复随机测试，并保留那些发现最重要的能量。这种方法将高精度方法的计算成本降低了几个数量级。这些方法一旦完全开发出来，将通过开源机制与社区分享。这些活动的结果正在用于教学课程，并通过出版物、研讨会和会议介绍进行传播。这些想法为Piecuch集团的成员提供了物理科学前沿的积极培训经验。这项研究解决了电子结构理论的关键挑战之一，即发展实用和系统改进的从头计算方案，旨在准确描述分子能量学。人们普遍认为，基于耦合簇理论的尺寸扩展方法是解决这一挑战的优秀候选人。然而，它一直是出了名的困难，将高于两体组件的集群运营商，需要实现一个定量的描述，而不运行到禁止高阶耦合集群计划的计算成本。所提出的方法解决了这个问题，允许一个获得准确的能量相当于高层次的耦合集群计算，即使当电子准简并和高于对激发变得显着，在一小部分的计算成本。它还保留了传统的单参考计算的黑箱字符，通过融合确定性的形式主义，简称为CC（P;Q）与随机配置相互作用和耦合簇蒙特卡罗方法。形式和算法的进步和有效的计算机实现将伴随着与光谱学，化学反应机制和动力学，催化相关的分子势能面的计算。这项工作为研究生和博士后研究员提供了重要的培训，正在开发的项目将与更广泛的理论界广泛分享。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

High-level coupled-cluster energetics by Monte Carlo sampling and moment expansions: Further details and comparisons

• DOI: 10.1063/5.0045468
• 发表时间: 2021-03-28
• 期刊: JOURNAL OF CHEMICAL PHYSICS
• 影响因子: 4.4
• 作者: Deustua, J. Emiliano;Shen, Jun;Piecuch, Piotr
• 通讯作者: Piecuch, Piotr

Quantum computation solves a half-century-old enigma: Elusive vibrational states of magnesium dimer found

量子计算解决了半个世纪之久的谜团：发现了镁二聚体难以捉摸的振动态

• DOI: 10.1126/sciadv.aay4058
• 发表时间: 2020
• 期刊: Science Advances
• 影响因子: 13.6
• 作者: Yuwono, Stephen H.;Magoulas, Ilias;Piecuch, Piotr
• 通讯作者: Piecuch, Piotr

Benchmarking the semi-stochastic CC( P ; Q ) approach for singlet–triplet gaps in biradicals

对双自由基中单重态-三重态间隙的半随机 CC( P ; Q ) 方法进行基准测试

• DOI: 10.1063/5.0100165
• 发表时间: 2022
• 期刊: The Journal of Chemical Physics
• 作者: Chakraborty, Arnab;Yuwono, Stephen H.;Deustua, J. Emiliano;Shen, Jun;Piecuch, Piotr
• 通讯作者: Piecuch, Piotr

Accelerating convergence of equation-of-motion coupled-cluster computations using the semi-stochastic CC( P ; Q ) formalism

使用半随机 CC( P ; Q ) 形式加速运动方程耦合簇计算的收敛

• DOI: 10.1080/00268976.2020.1817592
• 发表时间: 2020
• 期刊: Molecular Physics
• 影响因子: 1.7
• 作者: Yuwono, Stephen H.;Chakraborty, Arnab;Emiliano Deustua, J.;Shen, Jun;Piecuch, Piotr
• 通讯作者: Piecuch, Piotr

Recent developments in the general atomic and molecular electronic structure system

• DOI: 10.1063/5.0005188
• 发表时间: 2020-04-21
• 期刊: JOURNAL OF CHEMICAL PHYSICS
• 影响因子: 4.4
• 作者: Barca, Giuseppe M. J.;Bertoni, Colleen;Gordon, Mark S.
• 通讯作者: Gordon, Mark S.