HIGH-RESOLUTION INFRARED-SPECTROSCOPY OF PYRAZINE AND NAPHTHALENE IN A MOLECULAR-BEAM

The high resolution infrared spectrum of pyrazine and naphthalene were measured in a molecular beam in the vicinity of the C-H stretching tr ansition. The rotational structure in the spectrum of pyrazine from 30 65-3073 cm(-1) reveals that the C-H stretch is coupled to one other vi brational mode in the molecule. The mode coupling is manifested in the spectrum as two overlapping vibrational bands. Each of these two band s are well modeled by an asymmetric top/rigid rotor Hamiltonian. The l ack of any angular momentum dependence on the coupling indicates that the vibrations are coupled by an anharmonic mechanism. The magnitude o f the coupling matrix element was determined to be 0.36 cm(-1). The ro tational structure in the spectrum of naphthalene from 3063-3067 cm(-1 ) reveals that except for several local perturbations, the spectrum is well modeled by an asymmetric top/rigid rotor Hamiltonian. The local perturbations include transitions that are split into doublets as well as transitions that have been shifted from their expected positions. The magnitude of the average coupling matrix element for the doublets was determined to be 0.0016 cm(-1). A comparison between the vibration al mode coupling in pyrazine and naphthalene indicates that mode coupl ing does not correlate with the density of states in the two molecules .