Supporting data: Reaction barriers at metal surfaces computed using the random phase approximation: Can we beat DFT in the generalized gradient approximation?

Objective: Compute barrier heights for dissociative chemisorption of H2 on Al(110) and Cu(111) using- the random phase approximation in the adiabatic-connection fluctuation-dissipation theorem,- hybrid functionals and- density functional theory in the generalized gradient approximation.Method: Electronic structure calculations.Notes: The data provided here is the raw data required to reproduce results presented in publication sited under "Linked sources"<br>The data collection in the two databases (database_H2onCu_flat.db and database_H2onAl_flat.db) provides computed energies for dissociative chemisorption barriers and asymptotic geometries relevant to the dissociative chemisorption reaction of H2 on Al(110) and Cu(111). The energies were computed using density functional theory approaches (DFT) (including hybrid functionals) and the the random phase approximation in the adiabatic-connection fluctuation-dissipation theorem (ACFDT-RPA). All energies were obtained using the code VASP6. Energies have been obtained for various different parameters, including different functionals, different sampling of the Brillouin zone (k-points), different plane wave cutoffs (Ecut), different smearing parameters, different slab thicknesses, different vacuum thicknesses ect as specified in the databases. Taken together, the data can be used to determine well converged barrier heights for the given barrier geometry for different DFT functionals and ACFDT-RPA as described in the relevant publication (see "Linked sources") and analysis.tar.gz. The resulting barriers are summarized in barriers_summary.txt, together with additional values from literature (see file for references) and experimentally motivated references derived in the linked publication based on results from Refs. [1,2,3,4]. The barrier geometries are taken from Refs. [1,2].Additionally, the data collection contains densities of states as computed with PBE and GW at the transition state geometry for H2 dissociating on Al(110) and Cu(111) as computed with VASP and a density of states projected onto molecular orbitals computed in GPAW. These data are relevant to judge the influence of possible band misalignments in the DFT calculations.For all data presented, the data collection provides the required information to redo the calculations. See README for further information.Please contact the authors to obtain scripts used to produce the final plots in the linked publication.<br>[1] Powell, A. D.; Kroes, G.-J.; Doblhoff-Dier, K. Quantum Monte Carlo Calculations on Dissociative Chemisorption of H2 + Al(110): Minimum Barrier Heights and Their Comparison to DFT Values. <em>J. Chem. Phys.</em> <strong>2020</strong>, <em>153</em> (22), 224701. https://doi.org/10.1063/5.0022919.[2] Doblhoff-Dier, K.; Meyer, J.; Hoggan, P. E.; Kroes, G.-J. Quantum Monte Carlo Calculations on a Benchmark Molecule–Metal Surface Reaction: H₂ + Cu(111). <em>J. Chem. Theory Comput.</em> <strong>2017</strong>, <em>13</em> (7), 3208–3219. https://doi.org/10.1021/acs.jctc.7b00344.[3] Diaz et al, Science 326, 5954, 832 (2009), https://doi.org/10.1126/science.1178722[4] Powell et al, J. Phys. Chem. Lett. 2024, 15, 1, 307–315 (2024), https://doi.org/10.1021/acs.jpclett.3c02972<br>

研究目标：采用绝热连接涨落耗散定理（adiabatic-connection fluctuation-dissipation theorem, ACFDT）下的随机相近似（random phase approximation, RPA）、混合泛函以及广义梯度近似（generalized gradient approximation, GGA）框架下的密度泛函理论（density functional theory, DFT），计算H₂在Al(110)与Cu(111)表面的解离化学吸附能垒高度。
研究方法：电子结构计算。
数据集说明：本数据集提供了复现关联来源（Linked sources）中所列论文成果所需的原始数据。
本数据集包含两个数据库（database_H2onCu_flat.db与database_H2onAl_flat.db），其中存储了H₂在Al(110)及Cu(111)表面解离化学吸附反应相关的解离化学吸附能垒与渐近几何构型的计算能量。上述能量通过密度泛函理论方法（DFT，含混合泛函）以及ACFDT-RPA计算得到，所有计算均采用VASP6软件完成。计算过程中涵盖了数据库中列明的多种参数变量，包括不同泛函、布里渊区（Brillouin zone）的不同采样方式（k点）、不同平面波截断能（Ecut）、不同展宽参数、不同平板模型厚度以及不同真空层厚度等。整合上述数据，可针对给定的能垒几何构型，基于相关论文（详见关联来源（Linked sources））与analysis.tar.gz中的描述，针对不同DFT泛函与ACFDT-RPA方法求取收敛良好的能垒高度。最终得到的能垒信息汇总于barriers_summary.txt文件中，该文件同时包含来自文献的补充数值（详见文件内参考文献）以及关联论文中基于参考文献[1,2,3,4]的实验相关参考值。能垒几何构型取自参考文献[1,2]。
此外，本数据集还包含采用VASP计算的、H₂在Al(110)与Cu(111)表面解离过渡态几何构型下的PBE泛函与GW方法的态密度数据，以及通过GPAW计算的、投影到分子轨道上的态密度数据。此类数据可用于评估DFT计算中可能存在的能带错位带来的影响。
针对本数据集提供的全部数据，均附带了重新开展计算所需的完整信息，详细说明请参阅README文件。如需获取关联论文中用于生成最终图表的代码脚本，请联系数据集作者。
参考文献：
[1] Powell, A. D.; Kroes, G.-J.; Doblhoff-Dier, K. 针对H₂ + Al(110)解离化学吸附的量子蒙特卡洛计算：最小能垒高度及其与DFT计算结果的对比. 《Journal of Chemical Physics》, 2020, 153(22): 224701. https://doi.org/10.1063/5.0022919.
[2] Doblhoff-Dier, K.; Meyer, J.; Hoggan, P. E.; Kroes, G.-J. 基准分子-金属表面反应的量子蒙特卡洛计算：H₂ + Cu(111). 《Journal of Chemical Theory and Computation》, 2017, 13(7): 3208–3219. https://doi.org/10.1021/acs.jctc.7b00344.
[3] Diaz et al. 《Science》, 2009, 326(5954): 832. https://doi.org/10.1126/science.1178722
[4] Powell et al. 《The Journal of Physical Chemistry Letters》, 2024, 15(1): 307–315. https://doi.org/10.1021/acs.jpclett.3c02972