Mella Massimo
School of Chemistry, Cardiff University, Cardiff CF10 3AT, United Kingdom.
J Chem Phys. 2009 Sep 28;131(12):124309. doi: 10.1063/1.3239476.
In this work, collisions between rotating atomic clusters composed of Lennard-Jones (LJ(n)) particles and an identical projectile have been investigated by means of trajectory simulations as a function of the cluster angular momentum J and internal energy E, and for different values of the projectile impact parameter b and relative velocity v(p). As expected, the collision (P(c)(b)) and capture [or sticking P(s)(b)] probabilities are found to decay below unity for values of b larger than the average surface radius of the cluster, with dP/db being strongly dependent on v(p). Both P(c)(b) and P(s)(b), however, appear to be largely insensitive to the modulus of the cluster angular momentum |J| and only weakly dependent on E for collisions involving target clusters with a lifetime tau>100 ps. The latter findings are interpreted as indicating the absence of strong changes in the structure of the target as a function of |J| and E. The comparison between the dissociation lifetime (tau(dyn)) of the postcapture complexes (LJ(n+1)()) obtained continuing trajectories after monomer capture and the one computed from the fragmentation of statistically prepared clusters (tau(stat)) supports the validity of a two-step capture-dissociation model; similarly, the comparison between the average amount of energy exchanged during trajectories (DeltaE(dyn)) in the process LJ(n)+LJ-->LJ(n+1)()-->LJ(n)+LJ and the one predicted by statistical simulations (DeltaE(stat)) suggests a fast statistical energy redistribution in the collisional complex even for very short tau(dyn) (e.g., 40 ps). In the case of projectiles aimed at the edge of the cluster [(grazing collisions, P(c)(b)<1]; however, the time elapsed between formal collision and dissociation, tau(coll), is such that tau(coll)<tau(stat) and the trajectories indicate the presence of ballistic dynamics and of a weak energy exchange (DeltaE(coll)<DeltaE(dyn), with DeltaE(coll) being the average energy exchanged during collisions). The relevance of these results to the study of gas phase nucleation and to the possibility of building a fully microcanonical framework for its description is discussed.
在本研究中,通过轨迹模拟研究了由 Lennard-Jones(LJ(n))粒子组成的旋转原子团簇与相同射弹之间的碰撞,碰撞作为团簇角动量 J 和内能 E 的函数,并且针对射弹碰撞参数 b 和相对速度 v(p) 的不同值进行了研究。正如预期的那样,当 b 的值大于团簇的平均表面半径时,发现碰撞概率 P(c)(b) 和捕获[或粘附概率 P(s)(b)]低于 1,且 dP/db 强烈依赖于 v(p)。然而,对于寿命 τ>100 ps 的目标团簇的碰撞,P(c)(b) 和 P(s)(b) 似乎在很大程度上对团簇角动量的模量|J|不敏感,并且仅微弱地依赖于 E。后一发现被解释为表明目标结构不会随着|J|和 E 发生强烈变化。将单体捕获后继续轨迹得到的捕获后复合物(LJ(n + 1)())的解离寿命(τ(dyn))与通过统计制备的团簇的碎片化计算得到的解离寿命(τ(stat))进行比较,支持了两步捕获 - 解离模型的有效性;类似地,在 LJ(n)+LJ-->LJ(n + 1)()-->LJ(n)+LJ 过程中轨迹上交换的平均能量(ΔE(dyn))与统计模拟预测的能量(ΔE(stat))之间的比较表明,即使对于非常短的 τ(dyn)(例如 40 ps),碰撞复合物中也存在快速的统计能量重新分布。然而,对于瞄准团簇边缘的射弹[掠射碰撞,P(c)(b)<1],形式碰撞和解离之间经过的时间 τ(coll) 满足 τ(coll)<τ(stat),并且轨迹表明存在弹道动力学和微弱的能量交换(ΔE(coll)<ΔE(dyn),其中 ΔE(coll) 是碰撞期间交换的平均能量)。讨论了这些结果与气相成核研究的相关性以及构建用于描述它的完全微正则框架的可能性。