Molecule-Specific Uncertainty Quantification in Quantum Chemical Studies

Solving the electronic Schrodinger equation for changing nuclear coordinates provides access to the Born-Oppenheimer potential energy surface. This surface is the key starting point for almost all theoretical studies of chemical processes in electronic ground and excited states (including molecular structure prediction, reaction mechanism elucidation, molecular property calculations, quantum and molecular dynamics). Electronic structure models aim at a sufficiently accurate approximation of this surface. They have therefore become a cornerstone of theoretical and computational chemistry, molecular physics, and materials science. In this work, we elaborate on general features of approximate electronic structure models such as accuracy, efficiency, and general applicability in order to arrive at a perspective for future developments, of which a vanguard has already arrived. Our quintessential proposition is that meaningful quantum mechanical predictions for chemical phenomena require system-specific uncertainty information for each and every electronic structure calculation, if objective conclusions shall be drawn with confidence.

Automated summary

Electronic structure models are essential tools for theoretical studies of chemical phenomena, with importance placed on accuracy, efficiency, and general applicability. The key to future developments lies in providing system-specific uncertainty information for each electronic structure calculation.