Influence of the van der Waals interaction in the dissociation dynamics of N2 on W(110) from first principles.
Influence of the van der Waals interaction in the dissociation dynamics of N2 on W(110) from first principles.
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根据第一原理，N2 解离动力学中范德华相互作用对 W(110) 的影响。
DOI：
10.1063/1.4908060
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
M. Alducin
中科院分区：
文献类型：
--
作者：
L. Martin;L. Martin;J. I. Juaristi;J. I. Juaristi;J. I. Juaristi;M. Blanco;M. Blanco;R. Muiño;R. Muiño;M. Alducin;M. Alducin
采用从头计算分子动力学（AIMD）方法，研究了N2在W（110）表面解离吸附过程中的货车范德华相互作用（vdW）.目前，基于密度泛函理论（DFT）和半局部PW 91和RPBE [Hammer et al. Phys. Rev. B 59，7413（1999）]交换相关泛函在六维势能面上进行的现有经典动力学计算不能完全描述初始粘附系数对实验中发现的分子束入射条件的依赖性。N2在W（110）上的解离不仅对短分子-表面距离非常敏感，而且对大距离也非常敏感，其中vdW相互作用不包括在半局域DFT中，应该占主导地位。在这项工作中，我们进行了系统的研究解离吸附使用现有的非本地功能，包括vdW相互作用（vdw-功能）的选择。显然，在所有情况下，非局部相关项的列入有助于纠正不切实际的能量障碍，在大分子表面距离的RPBE中确定。在测试的vdw-泛函中，Dion等人的原始vdw-DF [Phys. Rev. Lett. 92，246401（2004）]和更远的vdW-DF 2也给出了过渡态的N2吸附能和能垒的充分描述，即，通常用于验证任何交换相关泛函的质量的属性。然而，我们的AIMD计算的结果，这是在不同的入射条件下进行的，因此广泛的探测系统的多构型势能面，似乎并不令人满意的初步静态分析建议。当将获得的解离概率与现有的实验数据进行比较时，所使用的vdw-泛函似乎都不能完全充分描述短距离和长距离下的N2/W（110）相互作用。
Using ab initio molecular dynamics (AIMD) calculations, we investigate the role of the van der Waals (vdW) interaction in the dissociative adsorption of N2 on W(110). Hitherto, existing classical dynamics calculations performed on six-dimensional potential energy surfaces based on density functional theory (DFT), and the semi-local PW91 and RPBE [Hammer et al. Phys. Rev. B 59, 7413 (1999)] exchange-correlation functionals were unable to fully describe the dependence of the initial sticking coefficient on the molecular beam incidence conditions as found in experiments. N2 dissociation on W(110) was shown to be very sensitive not only to short molecule-surface distances but also to large distances where the vdW interaction, not included in semilocal-DFT, should dominate. In this work, we perform a systematic study on the dissociative adsorption using a selection of existing non-local functionals that include the vdW interaction (vdW-functionals). Clearly, the inclusion of the non-local correlation term contributes in all cases to correct the unrealistic energy barriers that were identified in the RPBE at large molecule-surface distances. Among the tested vdW-functionals, the original vdW-DF by Dion et al. [Phys. Rev. Lett. 92, 246401 (2004)] and the ulterior vdW-DF2 give also an adequate description of the N2 adsorption energy and energy barrier at the transition state, i.e., of the properties that are commonly used to verify the quality of any exchange-correlation functional. However, the results of our AIMD calculations, which are performed at different incidence conditions and hence extensively probe the multi-configurational potential energy surface of the system, do not seem as satisfactory as the preliminary static analysis suggested. When comparing the obtained dissociation probabilities with existing experimental data, none of the used vdW-functionals seems to provide altogether an adequate description of the N2/W(110) interaction at short and large distances.
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影响因子：
8.6
作者：
I. Goikoetxea;Jörg Meyer;J. I. Juaristi;M. Alducin;Karsten Reuter
通讯作者：
I. Goikoetxea;Jörg Meyer;J. I. Juaristi;M. Alducin;Karsten Reuter
影响因子：
4.4
作者：
Carrasco, Javier;Liu, Wei;Tkatchenko, Alexandre
通讯作者：
Tkatchenko, Alexandre
影响因子：
4.4
作者：
Klimes, Jiri;Michaelides, Angelos
通讯作者：
Michaelides, Angelos
DOI：
10.1063/1.4894083
发表时间：
2014-09
期刊：
The Journal of chemical physics
影响因子：
--
作者：
G. Füchsel;J. Tremblay;P. Saalfrank
通讯作者：
G. Füchsel;J. Tremblay;P. Saalfrank