用机器学习同时预测量子化学高精度波函数和响应性质,速度更快、范围更广。
MōLe-Λ: Learning the Coupled-Cluster Response State for Energies, Gradients, and Properties

- 联合学习左右手振幅,从局域哈特里-福克轨道建模耦合簇响应态
- 在分子能量、力、偶极矩等10余种性质上达到耦合簇精度,计算速度提升数倍
- 适合需要高精度电子结构信息的材料与反应机理研究者
耦合簇(CC)理论是量子化学的黄金标准,但其高昂的计算成本限制了对精确能量、力和响应性质的常规访问。尽管右手振幅(T₁, T₂)决定相关波函数,许多重要可观测量还需左手振幅(Λ₁, Λ₂)。我们提出MōLe-Λ,是分子轨道学习(MōLe)的扩展,通过联合学习局域哈特里-福克分子轨道中的右手振幅(T₁, T₂)与左手振幅(Λ₁, Λ₂),实现全基组耦合簇单双激发(CCSD)响应态的预测。架构上,MōLe-Λ在原模型基础上增加Λ₁、Λ₂读出层,镜像匹配T₁、T₂的对称性约束,同时保持原始的等变轨道编码器、奇偶符号等变解码、局部性和规模可扩展性。该模型不仅能准确预测高质量的分子能量与力,还能同步恢复偶极矩、四极矩、极化率、电子密度及双电子可观测量(如双电子密度)。结果表明,相较于完整CCSD,MōLe-Λ进一步提升了速度优势,并大幅拓展了可计算性质范围,为关联量子化学提供了波函数级代理模型的新路径。
原文摘要 · Abstract (English)
Coupled-cluster (CC) theory is often considered the gold standard of quantum chemistry, but its high computational cost limits routine access to accurate energies, forces and response properties. While the right-hand $T$-amplitudes determine the correlated wavefunction, many practically important observables additionally require the left-hand $Λ$-amplitudes. We introduce MōLe-$Λ$, an extension of Molecular Orbital Learning (MōLe) that predicts the full ground-state coupled-cluster singles and doubles (CCSD) response state by jointly learning right-hand amplitudes $(T_1,T_2)$ and left-hand amplitudes $(Λ_1,Λ_2)$ from localized Hartree--Fock molecular orbitals. Architecturally, MōLe-$Λ$ extends MōLe with $Λ_1$ and $Λ_2$ readouts that mirror the symmetry constraints of the $T_1$ and $T_2$ heads, while preserving the original equivariant orbital encoder, odd sign-equivariant decoding, locality and size-extensivity. The resulting model yields accurate CC-quality energies and forces, while simultaneously recovering dipoles, quadrupoles, polarizabilities, the electron density, and 2-electron observables such as the pair density. We show that MōLe-$Λ$ further extends the speed advantage of MōLe over full CCSD while substantially expanding the accessible properties, providing a route to wavefunction-level surrogate models for correlated quantum chemistry.
Thank you to arXiv for use of its open access interoperability. PaperDance 不是 arXiv 官方产品;中文卡片由大模型生成,请以原文为准。