数据驱动的完全基集从最小辅助基的极限估计

IF 5.8 1区 化学 Q2 CHEMISTRY, PHYSICAL
Nicolas Grimblat,Gabriel Klassen,Guido Falk von Rudorff
{"title":"数据驱动的完全基集从最小辅助基的极限估计","authors":"Nicolas Grimblat,Gabriel Klassen,Guido Falk von Rudorff","doi":"10.1021/acs.jctc.6c01004","DOIUrl":null,"url":null,"abstract":"Quantum chemistry calculations are often performed using atom-centered basis sets, which are chosen to balance accuracy and cost. While they are systematically improvable, the total energy converges slowly with basis set size toward the complete basis set (CBS) limit. Common extrapolation methods require several intermediate-quality calculations to afford an estimate of the CBS energy. We propose a minimal complementary auxiliary basis set (CABS) baseline to estimate the CBS energy from a single quantum chemistry calculation in a minimal basis set via kernel ridge regression (KRR), which is more efficient than both direct and Δ-machine learning and 40× faster than triple-ζ single-point calculations. The spatial and alchemical gradients from minimal basis and minimal CABS are more accurate than double-ζ (DZ) calculations. We show that KRR on standard molecular representations can be improved by approximating atom-wise local kernels using Chebyshev polynomials, which allows us to train KRR models 10×–50× times faster on moderate compute resources, thereby enabling a data-driven approach toward the mean-field CBS, combining physical baselines capturing leading-order effects with data-efficient machine learning models.","PeriodicalId":45,"journal":{"name":"Journal of Chemical Theory and Computation","volume":"16 1","pages":""},"PeriodicalIF":5.8000,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Data-Driven Complete Basis Set Limit Estimates from a Minimal Auxiliary Basis\",\"authors\":\"Nicolas Grimblat,Gabriel Klassen,Guido Falk von Rudorff\",\"doi\":\"10.1021/acs.jctc.6c01004\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Quantum chemistry calculations are often performed using atom-centered basis sets, which are chosen to balance accuracy and cost. While they are systematically improvable, the total energy converges slowly with basis set size toward the complete basis set (CBS) limit. Common extrapolation methods require several intermediate-quality calculations to afford an estimate of the CBS energy. We propose a minimal complementary auxiliary basis set (CABS) baseline to estimate the CBS energy from a single quantum chemistry calculation in a minimal basis set via kernel ridge regression (KRR), which is more efficient than both direct and Δ-machine learning and 40× faster than triple-ζ single-point calculations. The spatial and alchemical gradients from minimal basis and minimal CABS are more accurate than double-ζ (DZ) calculations. We show that KRR on standard molecular representations can be improved by approximating atom-wise local kernels using Chebyshev polynomials, which allows us to train KRR models 10×–50× times faster on moderate compute resources, thereby enabling a data-driven approach toward the mean-field CBS, combining physical baselines capturing leading-order effects with data-efficient machine learning models.\",\"PeriodicalId\":45,\"journal\":{\"name\":\"Journal of Chemical Theory and Computation\",\"volume\":\"16 1\",\"pages\":\"\"},\"PeriodicalIF\":5.8000,\"publicationDate\":\"2026-10-19\",\"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://doi.org/10.1021/acs.jctc.6c01004\",\"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://doi.org/10.1021/acs.jctc.6c01004","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

量子化学计算通常使用以原子为中心的基集来执行,这是为了平衡准确性和成本而选择的。虽然它们具有系统的可改进性,但总能量随着基集的大小向完全基集(CBS)极限缓慢收敛。常见的外推方法需要几个中等质量的计算来提供对CBS能量的估计。我们提出了一个最小互补辅助基集(CABS)基线,通过核脊回归(KRR)从最小基集的单个量子化学计算中估计CBS能量,这比直接和Δ-machine学习更有效,比三重-ζ单点计算快40倍。最小基和最小CABS的空间和炼金术梯度比双ζ (DZ)计算更准确。我们表明,标准分子表示上的KRR可以通过使用Chebyshev多项式近似原子局部核来改进,这使我们能够在中等计算资源上以10×-50×倍的速度训练KRR模型,从而实现平均场CBS的数据驱动方法,将捕获领先顺序效应的物理基线与数据高效的机器学习模型相结合。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Data-Driven Complete Basis Set Limit Estimates from a Minimal Auxiliary Basis

Data-Driven Complete Basis Set Limit Estimates from a Minimal Auxiliary Basis
Quantum chemistry calculations are often performed using atom-centered basis sets, which are chosen to balance accuracy and cost. While they are systematically improvable, the total energy converges slowly with basis set size toward the complete basis set (CBS) limit. Common extrapolation methods require several intermediate-quality calculations to afford an estimate of the CBS energy. We propose a minimal complementary auxiliary basis set (CABS) baseline to estimate the CBS energy from a single quantum chemistry calculation in a minimal basis set via kernel ridge regression (KRR), which is more efficient than both direct and Δ-machine learning and 40× faster than triple-ζ single-point calculations. The spatial and alchemical gradients from minimal basis and minimal CABS are more accurate than double-ζ (DZ) calculations. We show that KRR on standard molecular representations can be improved by approximating atom-wise local kernels using Chebyshev polynomials, which allows us to train KRR models 10×–50× times faster on moderate compute resources, thereby enabling a data-driven approach toward the mean-field CBS, combining physical baselines capturing leading-order effects with data-efficient machine learning models.
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
小红书