The reactive dynamics of N₂ on W(100) has been investigated by means of quasi-classical trajectory calculations using an interpolated six-dimensional potential energy surface (PES) based on density functional theory energies obtained employing the vdW-DF2 functional. The dynamics are compared to those obtained using the PW91 functional and to experimental data. The results show that the new PES provides a significant improvement in the description of the reactivity in this system. We show that the long standing problem that constituted the large qualitative disagreement between the simulations performed with the PW91-PES and the experiments was due to the presence of energy barriers in the entrance channel that disappear when vdW forces are accounted for.

中文翻译：

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N ₂粘附在W（100）上的动力学：范德华相互作用的决定性作用†

N（_2）在W（100）上的反应动力学已通过准经典轨迹计算方法进行了研究，该计算方法使用基于内插六维势能面（PES）的密度函数理论能量，该能量是通过使用vdW-DF2函数获得的。将动力学与使用PW91功能获得的动力学和实验数据进行比较。结果表明，新的PES对该系统中反应性的描述提供了重大改进。我们表明，长期存在的问题构成了用PW91-PES执行的仿真与实验之间存在较大的定性分歧，这是由于在考虑vdW力时入口通道中存在的能垒消失了。