The versatile Bell-Evans-Polanyi (BEP) relation stipulates the kinetics of a reaction in terms of thermodynamics. Herein, we establish the BEP relation for the hydrogen evolution reaction (HER) from fundamental electrochemical principles leveraging the Butler-Volmer relation for a one-step, one-electron process and the transition state theory. Based on first-principles investigations of HER mechanisms on fourteen metal electrodes, we firmly justify the BEP relation solely using an easy-to compute hydrogen adsorption free energy and universal electrochemical constants.

中文翻译：

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从第一原理得出析氢反应的 Bell-Evans-Polanyi 关系

通用的贝尔-埃文斯-波兰尼 (BEP) 关系从热力学角度规定了反应动力学。在此，我们利用单步单电子过程的 Butler-Volmer 关系和过渡态理论，根据基本电化学原理建立了析氢反应 (HER) 的 BEP 关系。基于对 14 个金属电极上 HER 机制的第一性原理研究，我们仅使用易于计算的氢吸附自由能和通用电化学常数就坚定地证明了 BEP 关系。