Maximizing the hyperpolarizability of 1D potentials with multiple electrons

TL;DR

This study optimizes hyperpolarizabilities in 1D potentials with multiple electrons, revealing bounds and parameter sensitivities, which could inform the design of nonlinear optical materials.

Contribution

It introduces a simple parametrization for optimizing hyperpolarizabilities in multi-electron 1D potentials and analyzes the parameter space for physical insights.

Findings

Optimized hyperpolarizabilities approach constant bounds for N>8.

Two parameters suffice to reach near-optimal values.

Eigenvectors of the Hessian align with parameter basis vectors.

Abstract

We optimize the first and second intrinsic hyperpolarizabilities for a 1D piecewise linear potential dressed with Dirac delta functions for $N$ non-interacting electrons. The optimized values fall rapidly for $N>1$, but approach constant values of $\beta_{int}=0.40$, $\gamma_{int}^{+}=0.16$ and $\gamma_{int}^{-}=-0.061$ above $N\gtrsim8$. These apparent bounds are achieved with only 2 parameters with more general potentials achieving no better value. In contrast to previous studies, analysis of the hessian matrices of $\beta_{int}$ and $\gamma_{int}$ taken with respect to these parameters shows that the eigenvectors are well aligned with the basis vectors of the parameter space, indicating that the parametrization was well-chosen. The physical significance of the important parameters is also discussed.