The ionization behavior of the high Rydberg states of bis(eta(6)-benzene)chromium in the presence of ac and/or dc fields has been explored. The application of an ac scrambling field at the time of laser excitation lengthens the lifetime of the Rydberg state by almost two orders of magnitude. The lifetime enhancement by the scrambling field is much more effective for n < 100 than it is for n > 100 Rydberg states. The pulsed-field ionization of Rydberg states of n < 100 shows the typical diabatic ionization behavior for low n. The two distinct ionization behaviors observed for the relatively low (n=50-100) and high (n=100-200) Rydberg states suggest that the former originate from the optically accessed nf Rydberg series, whereas the latter are due to np Rydberg series. Based on the understanding of the ionization behavior of bis(eta(6)-benzene)chromium, the accurate ionization potential is deduced to give IP=5.4665 +/- 0.0003 eV. Optimization of the various electric field conditions greatly enhances the spectral sensitivity of the mass-analyzed threshold ionization (MATI) spectroscopy. The high-resolution MATI spectrum of the title molecule obtained here provides precise cationic vibrational frequencies for many skeletal and benzene ring modes. A number of vibrational modes are newly identified, and the ambiguity regarding to some mode assignments is now clearly resolved through the Frank-Condon analysis based on ab initio calculations. (c) 2007 American Institute of Physics.