Monte Carlo Studies of the Fundamental Limits of the Intrinsic Hyperpolarizability

The off-resonant hyperpolarizability is calculated using the dipole-free sum-over-stats expression from a randomly chosen set of energies and transition dipole moments that are forced to be consistent with the sum rules. The process is repeated so that the distribution of hyperpolarizabilities can be determined. We find this distribution to be a cycloid-like function. In contrast to variational techniques that when applied to the potential energy function yield an intrinsic hyperpolarizability less than 0.71, our Monte Carlo method yields values that approach unity. While many transition dipole moments are large when the calculated hyperpolarizability is near the fundamental limit, only two excited states dominate the hyperpolarizability - consistent with the three-level ansatz.Comment: 7 pages, 5 figure

Monte Carlo Studies of the Intrinsic Second Hyperpolarizability

The hyperpolarizability has been extensively studied to identify universal properties when it is near the fundamental limit. Here, we employ the Monte Carlo method to study the fundamental limit of the second hyperpolarizability. As was found for the hyperpolarizability, the largest values of the second hyperpolarizability approaches the calculated fundamental limit. The character of transition moments and energies of the energy eigenstates are investigated near the second hyperpolarizability's upper bounds using the missing state analysis, which assesses the role of each pair of states in their contribution. In agreement with the three-level ansatz, our results indicate that only three states (ground and two excited states) dominate when the second hyperpolarizability is near the limit.Comment: 8 pages, 7 figure

Compact Sum-Over-States Expression without Dipolar Terms for Calculating Nonlinear Susceptibilities

Using sum rules, the dipolar terms can be eliminated from the commonly-used sum-over-states (SOS) expression for nonlinear susceptibilities. This new dipole-free expression is more compact, converges to the same results as the common SOS equation, and is more appropriate for analyzing certain systems such as octupolar molecules. The dipole-free theory can be used as a tool for analyzing the uncertainties in quantum calculations of susceptibilities, can be applied to a broader set of quantum systems in the three-level model where the standard SOS expression fails, and more naturally leads to fundamental limits of the nonlinear susceptibilities.Comment: 6 pages and 4 figures Paper now in prin

Studies on optimizing potential energy functions for maximal intrinsic hyperpolarizability

We use numerical optimization to study the properties of (1) the class of one-dimensional potential energy functions and (2) systems of point charges in two-dimensions that yield the largest hyperpolarizabilities, which we find to be within 30% of the fundamental limit. We investigate the character of the potential energy functions and resulting wavefunctions and find that a broad range of potentials yield the same intrinsic hyperpolarizability ceiling of 0.709.Comment: 9 pages, 9 figure

Effect of a thin optical Kerr medium on a Laguerre-Gaussian beam

Using a generalized Gaussian beam decomposition method we determine the propagation of a Laguerre-Gaussian beam that has passed through a thin nonlinear optical Kerr medium. The orbital angular momentum per photon of the beam is found to be conserved while the component beams change. As an illustration of applications, we propose and demonstrate a z-scan experiment using an $LG_0^1$ beam and a dye-doped polymer film.Comment: 3 pages, 2 figures, corrected typo