Line strengths and transition dipole moment of the ν2 fundamental band of the methyl radical.

The line strengths of nine Q-branch lines in the ν2 fundamental band of the methyl radical in its ground electronic state have been measured by diode laser absorption spectroscopy. The vibration–rotation spectrum of methyl was recorded in a microwave discharge in ditertiary butyl peroxide heavily diluted in argon. The absolute concentration of the radical was determined by measuring its kinetic decay when the discharge was extinguished. The translational, rotational, and vibrational temperatures, also required to relate the line strengths to the transition dipole moment, were determined from relative integrated line intensities and from the Doppler widths of the lines after allowing for instrumental factors. The line strengths of the nine Q-branch lines were used to derive a more accurate value of the transition dipole moment of this band, μ2=0.215(25) D. Improved accuracy over earlier measurements of μ2 (derived from line strengths of single lines) was obtained by integrating over the complete line profile instead of measuring the peak absorption and assuming a Doppler linewidth to deduce the concentration. In addition, a more precise value for the rate constant for methyl radical recombination than available earlier was employed. The new value of μ2 is in very good agreement with high-quality ab initio calculations. Furthermore, the ratio of the transition dipole moments of the ν2 and ν3 fundamental bands in the gas phase is now in highly satisfactory agreement with the ratio determined for the condensed phase. © 2005 American Institute of Physics. [ABSTRACT FROM AUTHOR]