The accurate modeling of dissociative chemisorption of molecules on metal surfaces presents an exciting scientific challenge to theorists, and is practically relevant to modeling heterogeneously catalyzed reactive processes in computational catalysis. The first important scientific challenge in the field is that accurate barriers for dissociative chemisorption are not yet available from first principles methods. For systems that are not prone to charge transfer (for which the difference between the work function of the surface and the electron affinity of the molecule is less than 7 eV) this problem can be circumvented: chemically accurate barrier heights can be extracted with a semi-empirical version of density functional theory (DFT). However, a second important challenge is posed by systems that are prone to (full or partial) electron transfer from the surface to the molecule. For these systems the Born-Oppenheimer approximation breaks down, and currently no method of established accuracy exists for modeling the resulting effect of non-adiabatic energy dissipation on the dissociative chemisorption reaction. Because two problems exist for this class of reactions, a semi-empirical approach to computing barrier heights, which would demand that computed and experimental dissociative chemisorption probabilities match, is unlikely to work. This Perspective presents a vision on how these two problems may be solved. We suggest an approach in which parameterized density functionals are used as in the previous semi-empirical approach to DFT, but in which the parameters are based on calculations with first principles electronic structure methods. We also suggest that the diffusion Monte-Carlo (DMC) and the random phase approximation (RPA) probably are the best two first principles electronic structure methods to pursue in the framework of the approach that we call first-principles based DFT (FPB-DFT) – providing DMC and the RPA with a steppingstone towards benchmarking and future applications in computational catalysis. Probably the FPB density functional is best based on screened hybrid exchange in combination with non-local van der Waals correlation.There is a second paragraph we cannot at this stage include, but we feel it should be there, Please see the uploaded paper.

中文翻译：

---

两全其美的计算方法，用于金属表面难以建模的解离反应


分子在金属表面上的解离化学的准确建模对理论家提出了一个令人兴奋的科学挑战，并且与计算催化中的非均相催化反应过程的建模具有实际意义。该领域的第一个重要科学挑战是第一性原理方法尚无法获得解离化学吸附的准确屏障。对于不易发生电荷转移的系统（表面功函数与分子的电子亲和力之差小于 7 eV），可以避免这个问题：可以使用密度泛函理论 （DFT） 的半经验版本提取化学准确的势垒高度。然而，第二个重要挑战是容易发生（全部或部分）电子从表面转移到分子的系统。对于这些系统，Born-Oppenheimer 近似被打破，目前没有确定精度的方法来模拟非绝热能量耗散对解离化学吸附反应的结果影响。因为这类反应存在两个问题，所以计算势垒高度的半经验方法不太可能奏效，该方法要求计算和实验解离化学吸附概率匹配。本 Perspective 提出了如何解决这两个问题的愿景。我们建议一种方法，其中使用参数化密度泛函，就像之前的 DFT 半经验方法一样，但其中参数基于第一性原理电子结构方法的计算。 我们还建议，扩散蒙特卡洛 （DMC） 和随机相位近似 （RPA） 可能是在我们称为基于第一性原理的 DFT （FPB-DFT） 的方法框架中追求的最好的两种第一性原理电子结构方法——为 DMC 和 RPA 提供了通往计算催化基准测试和未来应用的垫脚石。可能 FPB 密度泛函最好基于筛选的混合交换与非局部范德华相关性的组合。我们现阶段无法包含第二段，但我们认为它应该在那里，请参阅上传的论文。