The near IR spectrum of the NO(X(2)Pi)-CH4 complex.

We report the first measurement of the near IR spectrum of the NO-CH(4) complex in the region of the first vibrational NO overtone transition in an IR-resonance enhanced multiphoton ionization double resonance experiment. The origin band is located at 3723.26 cm(-1), i.e., redshifted by 0.59 cm(-1) from the corresponding NO monomer frequency. The observed spectrum consists of two bands assigned to the origin band and the excitation of hindered rotation of the NO monomer in the complex similar to z-axis rotation. The spacing and the relative intensity of the bands are consistent with a structure in which NO resides preferentially in a position perpendicular to the intermolecular axis. The deviation from the linear configuration with C(3v) symmetry can be regarded as a Jahn-Teller (JT) distortion. Each band is dominated by two broad peaks with a few resolved rotational structures. The large spacing between the two peaks is indicative of significant angular momentum quenching, possibly another manifestation of the JT effect. The delay dependence between the IR and UV laser pulses reveals a lifetime of about 10 ns for the vibrationally excited complex due to vibrational predissociation. On the other hand, the linewidth of the narrowest spectral features indicates a much shorter excited state lifetime of about 100 ps, most likely due to intramolecular vibrational redistribution.