A quantum mechanical model of the upper bounds of the cascading contribution to the second hyperpolarizability

Abstract

Microscopic cascading of second-order nonlinearities between two molecules has been proposed to yield an enhanced third-order molecular nonlinear-optical response. In this contribution, we investigate the two-molecule cascaded second hyperpolarizability and show that it will never exceed the fundamental limit of a single molecule with the same number of electrons as the two-molecule system. We show the apparent divergence behavior of the cascading contribution to the second hyperpolarizability vanishes when properly taking into account the intermolecular interactions. Although cascading can never lead to a larger nonlinear-optical response than a single molecule, it provides alternative molecular design configurations for creating materials with large third-order susceptibilities that may be difficult to design into a single molecule.

13 pages, 9 figures, 1 table

References in corpus (4)

• Pushing the hyperpolarizability to the limit
• Studies on optimizing potential energy functions for maximal intrinsic hyperpolarizability
• A new dipole-free sum-over-states expression for the second hyperpolarizability
• A classical model of the upper bounds of the cascading contribution to the second hyperpolarizability

Cited by in corpus (5)

• Generalizing the correlated chromophore domain model of reversible photodegradation to include the effects of an applied electric field
• A classical model of the upper bounds of the cascading contribution to the second hyperpolarizability
• Lowest-order relativistic corrections to the fundamental limits of nonlinear-optical coefficients
• The Local Field Factor and Microscopic Cascading: A Self-Consistent Method Applied to Confined Systems of Molecules
• Modeling off-resonant nonlinear-optical cascading in mesoscopic thin films and guest-host molecular systems