Evolution from a molecular Rydberg gas to an ultracold plasma in a   seeded supersonic expansion of NO
  We report the spontaneous formation of a plasma from a gas of cold Rydberg molecules. Double-resonant laser excitation promotes nitric oxide, cooled to 1 K in a seeded supersonic molecular beam, to single Rydberg states extending as deep as 80 cm$^{-1}$ below the lowest ionization threshold. The density of excited molecules in the illuminated volume is as high as 1 x 10$^{13}$ cm$^{-3}$. This population evolves to produce prompt free electrons and a durable cold plasma of electrons and intact NO$^{+}$ ions. 
J. P. Morrison, C. J. Rennick, J. S. Keller, and E. R. Grant