The influence of the attractive well on near and non-resonant vibrational energy transfer in the gas phase: CO(v = 1) deactivated by methane deuteroisomers

A new N2–He intermolecular potential with vibrational coordinate dependence is presented. Rate constants for the vibrational deactivation of N2(v=1) by He in the gas phase have been calculated over the temperature range 5–300 K. Accurate values of the rate constants for this process are known down to 100 K. We have now extended these measurements down to 70 K for the deactivation of N214(v=1) by He4 and down to 50 K for the deactivation of N215(v=1) by He3. Agreement between the theoretically calculated and the experimentally determined rate constants is excellent with the calculated values reproducing the experimental measurements within their error bars. An investigation of the low impact energy regime is also presented. While this focuses on collision energies of less than 20 cm−1 and yields rate constants which are in a temperature region inaccessible to our experimental method, it gives further insights into the influence of the attractive well on vibrational energy transfer processes.

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Vibrational energy transfer between the isotopomers of carbon monoxide at low temperatures

Turnidge¹,

Reid²,

Barnes³

et al. 1998

The Journal of Chemical Physics

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Rate constants have been measured for vibration to vibration energy transfer from C12O16(v=1) to the first vibrationally excited state of both C13O16 (Δν̄=47 cm−1) and C13O18 (Δν̄=100 cm−1) using the infrared laser fluorescence technique over the temperature range 50 to 270 K in the gas phase and in liquid neon, deuterium and argon solutions. Fluorescence from C12O16(v=1) was filtered out, and the time-dependence of the fluorescence intensity from the other isotopomer used to determine the rate constants for energy transfer. The results for the two isotopomeric systems are markedly different. For that with the smaller energy mismatch, C12O16–C13O16, the rate constants increase with decrease in temperature from 270 to 80 K. This is shown to be consistent with near-resonant energy transfer mediated by transition dipole-transition dipole couplings. Below 80 K, the temperature dependence of the rate constants flattens. For the C12O16–C13O18 system, the rate constants decrease with decrease in temperature from 270 to 100 K, below which they increase with further decrease in temperature. The temperature dependence in the range 270 to 100 K is shown to be consistent with energy transfer mediated by a combination of by long range and short range forces. Below 100 K, the temperature dependence of the rate constants is governed by attractive forces which influence the collision pair during their encounter. The rate constants are compared with previous studies of near-resonant vibrational energy transfer in other systems at low temperatures.

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The influence of the attractive well on near and non-resonant vibrational energy transfer in the gas phase: CO(v = 1) deactivated by methane deuteroisomers

Cited by 3 publications

References 21 publications

The influence of the attractive well on near-resonant vibrational energy transfer in the gas phase: the importance of third body collisions

The influence of the attractive well on near-resonant vibrational energy transfer in the gas phase: the importance of third body collisions

Vibrational deactivation of N2(v=1) by inelastic collisions with He3 and He4: An experimental and a theoretical study

Vibrational energy transfer between the isotopomers of carbon monoxide at low temperatures

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