2026-10-13T09:39:10Z https://api.figshare.com/v2/oai

oai:figshare.com:article/33968565 2026-09-22T18:20:58Z category_146 category_7 category_15 category_873 category_45 category_734 category_811 portal_63 item_type_3 month_year_09_2026

Does Your Self-Consistent Field Program Know How Wrong It Is? Introducing Quantum Chemistry Uncertainty Propagation Anna Diaz Farias (25091403) Shalith C. Jayasekara (25091406) Jonathan M. Waldrop (5367062) Eric Weber (2378128) Theresa L. Windus (1425502) Ryan M. Richard (1299108) Space Science Medicine Neuroscience Chemical Sciences not elsewhere classified Sociology Biological Sciences not elsewhere classified Mathematical Sciences not elsewhere classified establish significant figures analytic error bars affine forms improve ab initio </ scf estimates uncertainty incomplete scf convergence full iterative self wave function systems tested point arithmetic numerical approximations mol compared interval bounds gaussian screening first end first applied direct approach consistent field also show Quantum chemistry relies on numerical approximations. Establishing the correctness and limits of these approximations traditionally requires laborious benchmarking. We introduce a more direct approach, quantum chemistry uncertainty propagation (QCUP), and apply it to a full iterative self-consistent field (SCF) calculation. QCUP-SCF estimates uncertainty from floating-point arithmetic, primitive-Gaussian screening, and incomplete SCF convergence, and propagates it to the final energy and density. Across all systems tested, predictions are typically within 1 kcal/mol compared to analytic error bars and within an order of magnitude of the true error  enough to establish significant figures and support runtime decision making. We also show how thresholded-affine forms improve on interval bounds by exploiting guaranteed error cancellation. This is, to our knowledge, the first end-to-end forward uncertainty quantification demonstration for an iterative <i>ab initio</i> method, and the first applied to both energy and wave function. 2026-09-22T00:00:00Z Dataset Dataset 10.1021/acs.jpclett.6c02837.s002 https://figshare.com/articles/dataset/Does_Your_Self-Consistent_Field_Program_Know_How_Wrong_It_Is_Introducing_Quantum_Chemistry_Uncertainty_Propagation/33968565 CC BY-NC 4.0