School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, UK.
Phys Chem Chem Phys. 2014 Jan 14;16(2):477-88. doi: 10.1039/c3cp53550a.
State-to-state differential cross sections are reported for rotationally inelastic scattering of fully state-selected ND3 (j(k)(±) = 1(1)(-)) with He. Experimental measurements are compared with full close-coupling quantum-mechanical scattering calculations that used an ab initio potential energy surface. Results are presented for final states up to j'(k')(±) = 7(7)(-) at a mean collision energy of 430 cm(-1). For selected final quantum states, the effect of collision energy on the differential cross sections is also explored in the range 230-720 cm(-1). For the experimental studies, a hexapole electrostatic lens was used for the j(k)(±) state-selection of ND3 molecules in their electronic and vibrational ground states in a molecular beam. This state-selected molecular beam was then crossed with a beam of He atoms. The velocities of inelastically scattered ND3 molecules in single j'(k')(±) states were obtained by velocity map imaging, and converted to differential cross sections in the centre-of-mass frame by density-to-flux transformation. The close-coupling calculations reproduce well the measured angular distributions. For small changes in the rotational angular momentum quantum number (j), the ND3 is predominantly forward scattered, but the scattering shifts to the sideways and backward directions as Δj increases. For scattering into a given j'(k')(±) state, cross-sections for collisions that conserve the ± symmetry associated with the ND3 inversion vibration are larger and generally more forward scattered than the corresponding symmetry-changing processes.
状态到状态微分截面报告为旋转非弹性散射完全状态选择 ND3(j(k)(±)= 1(1)(-))与氦。实验测量结果与全紧密耦合量子力学散射计算进行了比较,该计算使用了从头算势能面。结果显示,在平均碰撞能为 430 cm(-1)时,最终状态高达 j'(k')(±)= 7(7)(-)。对于选定的最终量子态,还在 230-720 cm(-1)范围内研究了碰撞能对微分截面的影响。对于实验研究,使用六极静电透镜对 ND3 分子在电子和振动基态中的 j(k)(±)态进行选择,形成分子束。然后将这种状态选择的分子束与一束氦原子交叉。通过速度映射成像获得了单个 j'(k')(±)态中单散射 ND3 分子的速度,并通过密度到通量转换将其转换为质心框架中的微分截面。紧密耦合计算很好地再现了测量的角分布。对于转动角动量量子数(j)的小变化,ND3 主要向前散射,但随着Δj 的增加,散射移向侧面和向后方向。对于散射到给定的 j'(k')(±)态,与 ND3 反转振动相关联的±对称性守恒的碰撞的截面较大,并且通常比相应的对称变化过程更向前散射。