Excited Pfaffians: Generalized Neural Wave Functions Across Structure and State

Nicholas Gao, Till Grutschus, Frank Noe, Stephan Günnemann
Proceedings of the 43rd International Conference on Machine Learning, PMLR 306:33184-33213, 2026.

Abstract

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 $\mathcal{O}(N_s^4)$-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.

Cite this Paper

BibTeX
@InProceedings{pmlr-v306-gao26j, title = {Excited Pfaffians: Generalized Neural Wave Functions Across Structure and State}, author = {Gao, Nicholas and Grutschus, Till and Noe, Frank and G\"{u}nnemann, Stephan}, booktitle = {Proceedings of the 43rd International Conference on Machine Learning}, pages = {33184--33213}, year = {2026}, editor = {Zhang, Tong and Dudik, Miroslav and Jaggi, Martin and Agarwal, Alekh and Li, Sharon and Schuurmans, Dale and Zhu, Jerry and Berkenkamp, Felix and Dong, Hanze and Bietti, Alberto}, volume = {306}, series = {Proceedings of Machine Learning Research}, month = {06--11 Jul}, publisher = {PMLR}, pdf = {https://raw.githubusercontent.com/mlresearch/v306/main/assets/gao26j/gao26j.pdf}, url = {https://proceedings.mlr.press/v306/gao26j.html}, abstract = {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 $\mathcal{O}(N_s^4)$-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.} }
Endnote
%0 Conference Paper %T Excited Pfaffians: Generalized Neural Wave Functions Across Structure and State %A Nicholas Gao %A Till Grutschus %A Frank Noe %A Stephan Günnemann %B Proceedings of the 43rd International Conference on Machine Learning %C Proceedings of Machine Learning Research %D 2026 %E Tong Zhang %E Miroslav Dudik %E Martin Jaggi %E Alekh Agarwal %E Sharon Li %E Dale Schuurmans %E Jerry Zhu %E Felix Berkenkamp %E Hanze Dong %E Alberto Bietti %F pmlr-v306-gao26j %I PMLR %P 33184--33213 %U https://proceedings.mlr.press/v306/gao26j.html %V 306 %X 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 $\mathcal{O}(N_s^4)$-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.
APA
Gao, N., Grutschus, T., Noe, F. & Günnemann, S.. (2026). Excited Pfaffians: Generalized Neural Wave Functions Across Structure and State. Proceedings of the 43rd International Conference on Machine Learning, in Proceedings of Machine Learning Research 306:33184-33213 Available from https://proceedings.mlr.press/v306/gao26j.html.

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