Maté B, Thibault F, Tejeda G, Fernández J M, Montero S
Instituto de Estructura de la Materia, CSIC Serrano 121, 28006 Madrid, Spain.
J Chem Phys. 2005 Feb 8;122(6):064313. doi: 10.1063/1.1850464.
We report an experimental determination of the k(00-->02) rate coefficient for inelastic H(2):H(2) collisions in the temperature range from 2 to 110 K based on Raman spectroscopy data in supersonic expansions of para-H(2). For this purpose a more accurate method for inverting the master equation of rotational populations is presented. The procedure permits us to reduce the measured k(00-->02) rate coefficient to the corresponding sigma(00-->02) cross section in the range of precollisional energy from 360 to 600 cm(-1). Numerical calculations of sigma(00-->02) carried out in the frame of the coupled channel method are also reported for different intermolecular potentials of H(2). A good agreement is found between the experimental cross section and the numerical one derived from Diep and Johnson's potential [J. Chem. Phys. 112, 4465 (2000)].
我们基于仲氢（para-H₂）在超声速膨胀中的拉曼光谱数据，报告了在2至110K温度范围内，非弹性H₂:H₂碰撞的k(00→02)速率系数的实验测定结果。为此，提出了一种更精确的反转转动布居主方程的方法。该程序使我们能够将测量的k(00→02)速率系数换算为预碰撞能量在360至600cm⁻¹范围内相应的σ(00→02)截面。还报告了在耦合通道方法框架下，针对不同H₂分子间势进行的σ(00→02)数值计算。实验截面与从Diep和Johnson势[《化学物理杂志》112, 4465 (2000)]导出的数值截面之间发现了良好的一致性。
