Abstract: Nuclear quantum effects (NQEs), including quantum tunneling and zero-point motion, are mostly relevant to hydrogen-bonded (H-boned) systems and other light elements materials. In particular, the quantum behavior of protons is quite prominent at room temperature or higher and has significant effects on chemical reactions. However, the accurate and quantitative description of NQEs on surface chemistry at the atomic scale has proven to be experimentally challenging. This review will first summarize the behaviors of NQEs and its influences on a wide range of scientific disciplines. Then, we will introduce the conventional spectroscopic and diffraction techniques and the emerging scanning probe microscopy (SPM), which allows the access to the degree of freedom of protons at atomic scale both in real and energy space. We will also review the research advances of NQEs of surface water based on these techniques and highlight how the quantum motion of protons influences and assists the surface heterogeneous catalysis of H-rich systems. What's more, the role of quantum tunneling of other elements besides hydrogen in on-surface reaction is also summarized. At last, further challenges and perspective directions of NQEs in surface chemistry are remarked.

Key words: surface chemistry, nuclear quantum effects, scanning probe microscopy, water, light elements