Rotational structure of a super-excited state of the NO molecule revealed by OODR-multiphoton laser spectroscopy.

The optical-optical double resonance time of flight (OODR-TOF) spectroscopy technique was employed to examine the 65,000-66,500 cm(-1) region of the nitric oxide spectrum. In this region, we detected the following three electronic states: E (2)Sigma(+) (nu = 2) (Rydberg state), B (2)Pi (nu = 23) (valence state), and L (2)Pi (nu = 4) (valence state). The rotational structure analysis of an unexpected band in the red part of the spectra revealed the presence of a new super-excited (2)Sigma(+) Rydberg state at approximately 13.3 eV, which was populated through a three-photon transition from the intermediate A (2)Sigma(+) (nu = 0) state. This super-excited state converges to the NO (a(3)Sigma(+)) ionic state with electronic configuration (1sigma)(2)(2sigma)(2)(3sigma)(2)(4sigma)(2)(5sigma)(2)(1pi)(3)(2pi)(1)(3ssigma)(1).