Why hyperpolarizabilities fall short of the fundamental quantum limits.

@article{Tripathy2004WhyHF,
  title={Why hyperpolarizabilities fall short of the fundamental quantum limits.},
  author={Kakoli Tripathy and Javier P{\'e}rez Moreno and Mark G. Kuzyk and Benjamin J Coe and Koen Clays and Anne Myers Kelley},
  journal={The Journal of chemical physics},
  year={2004},
  volume={121 16},
  pages={7932-45}
}
Quantum sum rules impose limits on the hyperpolarizability, beta. A survey of the largest second-order molecular susceptibilities finds what appears to be a universal gap between the experimental results and the fundamental limits. In this work, we use theory, linear spectroscopy, Raman spectroscopy, and measured values of beta (using hyper-Rayleigh scattering and Stark Spectroscopy) to show that this gap is due to an unfavorable arrangement of excited state energies. The question of whether… CONTINUE READING