Zhang Liang, Nitz Florian, Borodin Dmitriy, Wodtke Alec M, Guo Hua
Department of Chemistry and Chemical Biology, Center for Computational Chemistry, University of New Mexico, Albuquerque, New Mexico 87131, United States.
Institute of Physical Chemistry, Georg-August University, Göttingen 37077, Germany.
Precis Chem. 2025 Feb 6;3(6):319-325. doi: 10.1021/prechem.4c00099. eCollection 2025 Jun 23.
The ring polymer molecular dynamics (RPMD) rate theory, which is capable of handling nuclear quantum effects such as zero-point energy and tunneling, is applied to the recombinative desorption (RD) of adsorbed hydrogen atoms on a Pt(111) surface, a fundamental surface reaction crucial in heterogeneous catalysis. Recent experiments have provided highly accurate measurements of hydrogen RD rates, offering rare benchmarks for theoretical predictions. The RPMD rate coefficients of H RD on an experimentally calibrated first-principles potential energy surface closely match the experimental data within a factor of 2 at several temperatures. Importantly, our results reveal that the dominant nuclear quantum effect in this prototypic system is the reactant zero-point energy, rather than tunneling.
环聚合物分子动力学（RPMD）速率理论能够处理诸如零点能和隧穿等核量子效应，被应用于Pt(111)表面吸附氢原子的复合脱附（RD）过程，这是多相催化中一个至关重要的基本表面反应。近期的实验提供了高精度的氢RD速率测量结果，为理论预测提供了难得的基准。在经过实验校准的第一性原理势能面上，氢RD的RPMD速率系数在几个温度下与实验数据紧密匹配，误差在2倍以内。重要的是，我们的结果表明，在这个原型系统中，占主导地位的核量子效应是反应物零点能，而非隧穿。
