Excited Pfaffians: Generalized Neural Wave Functions Across Structure and State

AI4S QNN Other AI4S
变分蒙特卡洛(VMC)中的神经网络波函数已在高精度表征基态与激发态方面取得巨大成功。然而,若要使不同量子态之间的重叠积分达到足够的数值精度,就必须随所考虑的态数增加而相应提升蒙特卡洛采样数,从而导致计算成本显著上升。为此,我们提出一种近乎恒定采样规模的新方法——多态重要性采样(Multi-State Importance Sampling, MSIS),该方法利用所有量子态共同产生的样本,来估计任意两个态之间的两两重叠积分。为高效地对所有样本同时评估全部量子态,我们引入了“激发Pfaffian”(Excited Pfaffians)这一新型波函数结构。该结构受哈特里–福克(Hartree–Fock)理论启发,可在单个神经网络中统一表征多个量子态。此外,“激发Pfaffian”本身亦可作为广义波函数使用,使单一模型能够刻画多态势能面。在碳二聚体(C₂)体系上,我们的方法在保持与自然激发态相同、随态数 \(N_s\) 呈四次方增长(即 \(O(N_s^4)\))的标度律的同时,训练速度提升逾200倍,并能建模比以往多50%的激发态。得益于优异的计算复杂度标度特性,我们成为首个借助神经网络完整求解铍原子(Be)所有不同能级的研究团队。最后,我们进一步证实:单个波函数即可跨多种分子体系,统一表征其各自的激发态。
Neural-network wave functions in Variational Monte Carlo (VMC) have achieved great success in accurately representing both ground and excited states. However, achieving sufficient numerical accuracy in state overlaps requires increasing the number of Monte Carlo samples, and consequently the computational cost, with the number of states. We present a nearly constant sample-size approach, Multi-State Importance Sampling (MSIS), that leverages samples from all states to estimate pairwise overlap. To efficiently evaluate all states for all samples, we introduce Excited Pfaffians. Inspired by Hartree-Fock, this architecture represents many states within a single neural network. Excited Pfaffians also serve as generalized wave functions, allowing a single model to represent multi-state potential energy surfaces. On the carbon dimer, we match the $O(N_s^4)$-scaling natural excited states while training $>200\times$ faster and modeling 50\% more states. Our favorable scaling enables us to be the first to use neural networks to find all distinct energy levels of the beryllium atom. Finally, we demonstrate that a single wave function can represent excited states across various molecules.
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