Time-resolved Fourier transform infrared spectroscopy of optically pumped carbon monoxide

• Published in: Chemical physics Vol. 256; no. 3; pp. 315 - 331
• Main Authors: Plönjes, Elke, Palm, Peter, Chernukho, Andrey P., Adamovich, Igor V., William Rich, J.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15.06.2000
• ISSN: 0301-0104
• DOI: 10.1016/S0301-0104(00)00096-3

The paper discusses measurements of vibration-to-vibration (V–V) energy transfer rates for CO–CO using time-resolved step-scan Fourier transform infrared spectroscopy of optically pumped carbon monoxide. In the experiments, time evolution of all vibrational states of carbon monoxide excited by a CO laser and populated by V–V processes (up to v∼40) is monitored simultaneously. The V–V rates are inferred from these data using a kinetic model that incorporates spatial power distribution of the focused laser beam, transport processes, and multi-quantum V–V processes. Although the model predictions agree well with the time-dependent step-scan relaxation data, there is variance between the model predictions and the up-pumping data, however. Comparison of calculations using two different sets of V–V rates with experimental spectra showed that the use of the semi-empirical V–V rates of DeLeon and Rich provides better agreement with experiment. It is also shown that the multi-quantum V–V rates among high vibrational quantum numbers, calculated by Cacciatore and Billing, are substantially overpredicted. The results provide some new insight into nonequilibrium vibrational kinetics, and also demonstrate the capabilities of the step-scan Fourier transform spectroscopy for time-resolved studies of molecular energy transfer processes and validation of theoretical rate models.