The infrared spectra of the weakly bound complexes Kr-CO and Xe-CO have bee
n studied in the region of the CO stretching vibration (4.7 mu m) using a h
igh-resolution tuneable diode laser probe. The complexes were observed in a
long path (200 m) low temperature (76 K) gas cell (Kr-CO) and in a pulsed
supersonic jet expansion (Kr-CO and Xe-CO). Previous long path cell measure
ments on these complexes at lower resolution analysed only the K = 0 and 1
stacks of rotational levels in the ground intermolecular vibrational state.
The new data extend up to K = 3 (Xe-CO) or 4 (Kr-CO), and also include K =
0 and 1 stacks in the excited bending state, nu(2) = 1. The bending freque
ncies for Kr-CO and Xe-CO (in the nu(CO) = 1 upper state) were determined t
o be 13.156 cm(-1) and 13.794 cm(-1), respectively. Detailed molecular para
meters were determined to describe the rotational energy levels of each com
plex using a simple empirical Hamiltonian. These results enable parameters
to be compared for the entire series of rare gas-carbon monoxide complexes,
from He-CO to Xe-CO. Also they will guide the future development and evalu
ation of accurate intermolecular potential energy surfaces for Kr-CO and Xe
-CO.