Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, 06123 Perugia, Italy.
J Chem Phys. 2014 Mar 28;140(12):124318. doi: 10.1063/1.4869595.
Molecular beam scattering experiments have been performed to study the effect of long-range anisotropic forces on the collision dynamics of two small polar molecules. The main focus of this paper is on water, but also ammonia and hydrogen sulphide molecules have been investigated, and some results will be anticipated. The intermolecular distances mainly probed are of the order of 1 nm and therefore much larger than the molecular dimensions. In particular, we have found that the natural electric field gradient, generated by different spatial orientations of the permanent electric dipoles, is able to promote the transformation of free rotations into coupled pendular states, letting the molecular partners involved in the collision complex swinging to and fro around the field direction. This long-ranged concerted motion manifested itself as large increases of the magnitude of the total integral cross section. The experimental findings and the theoretical treatment developed to shed light on the details of the process suggest that the transformation from free rotations to pendular states depends on the rotational level of both molecules, on the impact parameter, on the relative collision velocity, on the dipole moment product and occurs in the time scale of picoseconds. The consequences of this intriguing phenomenon may be important for the interpretation and, in perspective, for the control of elementary chemical and biological processes, given by polar molecules, ions, and free radicals, occurring in several environments under various conditions.
分子束散射实验已被用于研究长程各向异性力对两个小极性分子碰撞动力学的影响。本文的主要重点是水,但也研究了氨和硫化氢分子,并且预测了一些结果。主要探测的分子间距离约为 1nm,因此远大于分子尺寸。特别是,我们发现由永久电偶极子的不同空间取向产生的自然电场梯度能够促进自由旋转转化为耦合摆振状态,使参与碰撞复合物的分子伴侣在电场方向周围来回摆动。这种长程协同运动表现为总积分截面的大幅度增加。实验结果和为揭示过程细节而开发的理论处理表明,从自由旋转到摆振状态的转变取决于两个分子的旋转能级、碰撞参数、相对碰撞速度、偶极矩乘积,并在皮秒时间尺度上发生。这种有趣现象的后果对于解释和从长远来看对于控制由极性分子、离子和自由基在各种条件下发生的几种环境中的基本化学和生物过程可能很重要。