Journal of Chemical Physics, Vol.109, No.14, 5914-5920, 1998
Rotationally resolved IR spectroscopy of ammonia trapped in cold helium clusters
Infrared molecular beam depletion spectroscopy of ammonia molecules embedded in large He clusters has been studied in the spectral region of the ammonia umbrella mode from 940 to 1060 cm(-1). The transitions between the lowest rotational energy levels could be resolved. By fitting the spectrum with the Hamiltonian of a free rotor, we observe a large shift of the vibrational frequency of 17.4 cm(-1) to the blue, an effective decrease of the rotational constant B by 24%, and a reduction of the tunneling splitting by 31% in the excited and 75% in the ground state. This implies an unusually large interaction between the host cluster and the umbrella motion of the ammonia molecule, an intermediate influence on the rotation and also a large perturbation of the inversion by the helium environment.
Keywords:INTEGRAL MONTE-CARLO, INFRARED-SPECTROSCOPY, VIBRATIONALSPECTROSCOPY, HOST CLUSTERS, HE-4 CLUSTERS, SF6, COMPLEXES;MOLECULES, TEMPERATURE, INVERSION