多项式标度局部活动空间幺正选择性耦合簇单双。

IF 5.5 1区 化学 Q2 CHEMISTRY, PHYSICAL
Shreya Verma, Ruhee D’Cunha, Abhishek Mitra, Matthew Hermes, Stephen K. Gray, Matthew Otten* and Laura Gagliardi*, 
{"title":"多项式标度局部活动空间幺正选择性耦合簇单双。","authors":"Shreya Verma,&nbsp;Ruhee D’Cunha,&nbsp;Abhishek Mitra,&nbsp;Matthew Hermes,&nbsp;Stephen K. Gray,&nbsp;Matthew Otten* and Laura Gagliardi*,&nbsp;","doi":"10.1021/acs.jctc.5c00745","DOIUrl":null,"url":null,"abstract":"<p >We present a polynomial-scaling algorithm for the localized active space unitary selective coupled cluster singles and doubles (LAS-USCCSD) method. In this approach, cluster excitations are selected based on a threshold ϵ determined by the absolute gradients of the LAS-UCCSD energy with respect to cluster amplitudes. Using the generalized Wick’s theorem for multireference wave functions, we derive the gradient expression as a polynomial function of one-, two-, and three-body reduced density matrices and 1- and 2-electron integrals, valid for any multireference wave function. The resulting gradient implementation exhibits a memory scaling of <i></i><math><mi>O</mi></math>(<i>N</i><sup>6</sup>), with <i>N</i> spin orbitals in the combined active space of all fragments. The variational quantum eigensolver is used to optimize the selected cluster excitations on a quantum simulator. By plotting the energy error, defined as the difference between the LAS-USCCSD and corresponding CASCI energies, against the inverse cluster amplitude selection threshold (ϵ<sup>–1</sup>) for polyene chains containing 2 to 5 π-bond units, we establish a relationship between the energy error and the threshold. To further validate the accuracy of LAS-USCCSD, we computed the cis–trans isomerization energy of stilbene (a 20-qubit system) and the magnetic coupling constant of the tris-hydroxo-bridged chromium dimer [Cr<sub>2</sub>(OH)<sub>3</sub>(NH<sub>3</sub>)<sub>6</sub>]<sup>3+</sup> (evaluated as both 12- and 20-qubit systems) using the Qiskit-Qulacs simulator. Assessing such examples is important to determine the practical feasibility of quantum simulations for chemically realistic systems. Toward this goal, with the LAS-USCCSD algorithm we estimated the quantum resources required for simulating an active space of (30e,22o) in [Cr<sub>2</sub>(OH)<sub>3</sub>(NH<sub>3</sub>)<sub>6</sub>]<sup>3+</sup>, a size that remains beyond the reach of current quantum simulators for accurate treatment.</p>","PeriodicalId":45,"journal":{"name":"Journal of Chemical Theory and Computation","volume":"21 15","pages":"7460–7470"},"PeriodicalIF":5.5000,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Polynomial Scaling Localized Active Space Unitary Selective Coupled Cluster Singles and Doubles\",\"authors\":\"Shreya Verma,&nbsp;Ruhee D’Cunha,&nbsp;Abhishek Mitra,&nbsp;Matthew Hermes,&nbsp;Stephen K. Gray,&nbsp;Matthew Otten* and Laura Gagliardi*,&nbsp;\",\"doi\":\"10.1021/acs.jctc.5c00745\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >We present a polynomial-scaling algorithm for the localized active space unitary selective coupled cluster singles and doubles (LAS-USCCSD) method. In this approach, cluster excitations are selected based on a threshold ϵ determined by the absolute gradients of the LAS-UCCSD energy with respect to cluster amplitudes. Using the generalized Wick’s theorem for multireference wave functions, we derive the gradient expression as a polynomial function of one-, two-, and three-body reduced density matrices and 1- and 2-electron integrals, valid for any multireference wave function. The resulting gradient implementation exhibits a memory scaling of <i></i><math><mi>O</mi></math>(<i>N</i><sup>6</sup>), with <i>N</i> spin orbitals in the combined active space of all fragments. The variational quantum eigensolver is used to optimize the selected cluster excitations on a quantum simulator. By plotting the energy error, defined as the difference between the LAS-USCCSD and corresponding CASCI energies, against the inverse cluster amplitude selection threshold (ϵ<sup>–1</sup>) for polyene chains containing 2 to 5 π-bond units, we establish a relationship between the energy error and the threshold. To further validate the accuracy of LAS-USCCSD, we computed the cis–trans isomerization energy of stilbene (a 20-qubit system) and the magnetic coupling constant of the tris-hydroxo-bridged chromium dimer [Cr<sub>2</sub>(OH)<sub>3</sub>(NH<sub>3</sub>)<sub>6</sub>]<sup>3+</sup> (evaluated as both 12- and 20-qubit systems) using the Qiskit-Qulacs simulator. Assessing such examples is important to determine the practical feasibility of quantum simulations for chemically realistic systems. Toward this goal, with the LAS-USCCSD algorithm we estimated the quantum resources required for simulating an active space of (30e,22o) in [Cr<sub>2</sub>(OH)<sub>3</sub>(NH<sub>3</sub>)<sub>6</sub>]<sup>3+</sup>, a size that remains beyond the reach of current quantum simulators for accurate treatment.</p>\",\"PeriodicalId\":45,\"journal\":{\"name\":\"Journal of Chemical Theory and Computation\",\"volume\":\"21 15\",\"pages\":\"7460–7470\"},\"PeriodicalIF\":5.5000,\"publicationDate\":\"2025-07-16\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Chemical Theory and Computation\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.jctc.5c00745\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical Theory and Computation","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jctc.5c00745","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0

摘要

提出了一种局部有源空间幺正选择性耦合簇单双元(LAS-USCCSD)方法的多项式标度算法。在这种方法中,簇激发是基于一个阈值λ来选择的,这个阈值λ由LAS-UCCSD能量相对于簇振幅的绝对梯度决定。利用多参考波函数的广义Wick定理,我们导出了梯度表达式作为一体、二体和三体简化密度矩阵的多项式函数以及1电子和2电子积分,适用于任何多参考波函数。所得到的梯度实现显示出0 (N6)的内存缩放,在所有片段的组合有效空间中具有N个自旋轨道。利用变分量子特征求解器对量子模拟器上所选的簇激励进行了优化。通过绘制含有2 ~ 5 π键单元的多烯链的能量误差(定义为LAS-USCCSD与相应CASCI能量之差)与反簇幅选择阈值(ϵ-1)的关系,我们建立了能量误差与阈值之间的关系。为了进一步验证LAS-USCCSD的准确性,我们使用Qiskit-Qulacs模拟器计算了二苯乙烯(20量子位体系)的顺反异构化能和三羟基桥接铬二聚体[Cr2(OH)3(NH3)6]3+(评估为12和20量子位体系)的磁耦合常数。评估这些例子对于确定量子模拟化学现实系统的实际可行性非常重要。为了实现这一目标,我们使用LAS-USCCSD算法估计了模拟[Cr2(OH)3(NH3)6]3+中(30e, 220)的活动空间所需的量子资源,这一大小仍然超出了当前量子模拟器的精确处理范围。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Polynomial Scaling Localized Active Space Unitary Selective Coupled Cluster Singles and Doubles

Polynomial Scaling Localized Active Space Unitary Selective Coupled Cluster Singles and Doubles

We present a polynomial-scaling algorithm for the localized active space unitary selective coupled cluster singles and doubles (LAS-USCCSD) method. In this approach, cluster excitations are selected based on a threshold ϵ determined by the absolute gradients of the LAS-UCCSD energy with respect to cluster amplitudes. Using the generalized Wick’s theorem for multireference wave functions, we derive the gradient expression as a polynomial function of one-, two-, and three-body reduced density matrices and 1- and 2-electron integrals, valid for any multireference wave function. The resulting gradient implementation exhibits a memory scaling of O(N6), with N spin orbitals in the combined active space of all fragments. The variational quantum eigensolver is used to optimize the selected cluster excitations on a quantum simulator. By plotting the energy error, defined as the difference between the LAS-USCCSD and corresponding CASCI energies, against the inverse cluster amplitude selection threshold (ϵ–1) for polyene chains containing 2 to 5 π-bond units, we establish a relationship between the energy error and the threshold. To further validate the accuracy of LAS-USCCSD, we computed the cis–trans isomerization energy of stilbene (a 20-qubit system) and the magnetic coupling constant of the tris-hydroxo-bridged chromium dimer [Cr2(OH)3(NH3)6]3+ (evaluated as both 12- and 20-qubit systems) using the Qiskit-Qulacs simulator. Assessing such examples is important to determine the practical feasibility of quantum simulations for chemically realistic systems. Toward this goal, with the LAS-USCCSD algorithm we estimated the quantum resources required for simulating an active space of (30e,22o) in [Cr2(OH)3(NH3)6]3+, a size that remains beyond the reach of current quantum simulators for accurate treatment.

求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
Journal of Chemical Theory and Computation
Journal of Chemical Theory and Computation 化学-物理:原子、分子和化学物理
CiteScore
9.90
自引率
16.40%
发文量
568
审稿时长
1 months
期刊介绍: The Journal of Chemical Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere. Papers reporting new theories, methodology, and/or important applications in quantum electronic structure, molecular dynamics, and statistical mechanics are appropriate for submission to this Journal. Specific topics include advances in or applications of ab initio quantum mechanics, density functional theory, design and properties of new materials, surface science, Monte Carlo simulations, solvation models, QM/MM calculations, biomolecular structure prediction, and molecular dynamics in the broadest sense including gas-phase dynamics, ab initio dynamics, biomolecular dynamics, and protein folding. The Journal does not consider papers that are straightforward applications of known methods including DFT and molecular dynamics. The Journal favors submissions that include advances in theory or methodology with applications to compelling problems.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信