Temperature dependence of pressure broadening of NH₃ perturbed by H₂ and N₂

The temperature dependence of pressure broadening of 134 rovibrational transitions of several branches in the ν₄ and 2ν₂ bands of ammonia perturbed by H₂ and N₂ has been measured using a high-resolution Fourier transform spectrometer. The temperature range covered during the experiments was between 235 and 296K. The pressure-broadening linewidths were obtained using the method of multipressure fitting to the measured shapes of the lines. These broadenings were also calculated using a semiclassical model leading to a reasonable agreement with the observations and reproduces well the strong systematic experimental J and K quantum number dependencies. The retrieved values of the linewidths, along with those previously determined from the spectra at room temperature, were used to derive the temperature dependence of both H₂ and N₂ broadening of NH₃ lines. The broadening coefficients were shown to fit closely the well-known exponential law. For both experimental and theoretical results, the temperature exponent n has been obtained. Careful inspection of the experimental values shows that, contrary to the linewidths, the coefficient n is nearly K independent within each J multiplet. Also for a given J it does not seem to exhibit any noticeable variation with the type of rotational transition. On the other hand, the calculated n values exhibit a strong J and K systematic dependencies. n increases with K for a given J, decreases with J for a given K and are independent of the type of rotational transition.