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
利用基于绝热连接涨落耗散定理（Adiabatic-Connection Fluctuation-Dissipation Theorem, ACFDT）的随机相近似（Random Phase Approximation, RPA）、杂化泛函以及广义梯度近似（Generalized Gradient Approximation, GGA）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势垒高度。

### 研究方法
电子结构计算。

### 备注
本数据集提供了复现标注为「关联来源」的论文结果所需的原始数据。

两个数据库（database_H2onCu_flat.db 与 database_H2onAl_flat.db）收录的数据，为H₂在Al(110)和Cu(111)表面发生解离化学吸附反应相关的解离化学吸附势垒及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，包含杂化泛函）以及基于ACFDT的随机相近似（ACFDT-RPA）计算得到，全部计算均使用VASP6代码完成。

计算过程涵盖多种不同参数，具体包括不同泛函、布里渊区采样（k点）、不同平面波截断能（Ecut）、不同展宽参数、不同平板厚度、不同真空层厚度等，详细参数说明详见各数据库。结合相关文献（见「关联来源」）所述，本数据集可针对给定势垒几何构型，确定不同DFT泛函及ACFDT-RPA方法下收敛性良好的势垒高度。上述计算得到的势垒结果，与文献补充值（详见文件内参考文献）以及基于参考文献[1,2,3,4]推导得到的实验参考值，一并汇总于barriers_summary.txt中。本数据集采用的势垒几何构型取自参考文献[1,2]。

此外，本数据集还包含两类态密度（Density of States, DOS）数据：一是使用PBE泛函与GW方法，针对H₂在Al(110)与Cu(111)表面解离的过渡态几何构型计算得到的态密度；二是使用GPAW计算的投影至分子轨道的态密度。上述数据可用于评估DFT计算中可能存在的能带失配影响。

对于本数据集提供的全部数据，均包含复现计算所需的完整信息，详细说明请参阅README文件。如需获取用于绘制关联论文中最终图表的脚本，请联系论文作者。

#### 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：最小势垒高度及其与DFT结果的对比. 《化学物理杂志》(J. Chem. Phys.) 2020, 153(22), 224701. https://doi.org/10.1063/5.0022919.
[2] Doblhoff-Dier, K.; Meyer, J.; Hoggan, P. E.; Kroes, G.-J. 针对基准分子-金属表面反应的量子蒙特卡洛计算：H₂ + Cu(111). 《化学理论与计算杂志》(J. Chem. Theory Comput.) 2017, 13(7), 3208–3219. https://doi.org/10.1021/acs.jctc.7b00344.
[3] Diaz et al, 《科学》(Science) 326, 5954, 832 (2009), https://doi.org/10.1126/science.1178722
[4] Powell et al, 《物理化学快报杂志》(J. Phys. Chem. Lett.) 2024, 15, 1, 307–315 (2024), https://doi.org/10.1021/acs.jpclett.3c02972