Computer simulations of the linewidth of the Raman <i>Q</i>-branch in fluid nitrogen

Abstract

By means of molecular dynamical simulations, the width of the Raman line in fluid N2 is calculated at room temperature and pressures up to the melting line. The results are compared with experimental results for the linewidth and for the dephasing time. Detailed information is given about the relaxation mechanism of the vibrational frequency. For instance, a marked influence of the vibration-rotation coupling is seen, in particular at high pressures. Moreover, the time correlation function of the frequency reveals a long time behavior at high pressures. From a comparison of the simulated change in vibrational frequency as a function of pressure with experimental data for the line shift, an estimate is made for the contribution of the so-called ‘‘attractive part’’ to that shift.