Exact Fundamental Limits of the First and Second Hyperpolarizabilities.

Nonlinear optical interactions of light with materials originate in the microscopic response of the molecular constituents to excitation by an optical field, and are expressed by the first (β) and second (γ) hyperpolarizabilities. Upper bounds to these quantities were derived seventeen years ago using approximate, truncated state models that violated completeness and unitarity, and far exceed those achieved by potential optimization of analytical systems. This Letter determines the fundamental limits of the first and second hyperpolarizability tensors using Monte Carlo sampling of energy spectra and transition moments constrained by the diagonal Thomas-Reiche-Kuhn (TRK) sum rules and filtered by the off-diagonal TRK sum rules. The upper bounds of β and γ are determined from these quantities by applying error-refined extrapolation to perfect compliance with the sum rules. The method yields the largest diagonal component of the hyperpolarizabilities for an arbitrary number of interacting electrons in any number of dimensions. The new method provides design insight to the synthetic chemist and nanophysicist for approaching the limits. This analysis also reveals that the special cases which lead to divergent nonlinearities in the many-state catastrophe are not physically realizable.