Malpathak Shreyas, Ananth Nandini
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, United States.
J Phys Chem Lett. 2024 Jan 25;15(3):794-801. doi: 10.1021/acs.jpclett.3c03041. Epub 2024 Jan 17.
The vibrational relaxation of NO molecules scattering from a Au(111) surface has served as the focus of efforts to understand nonadiabatic energy transfer at metal-molecule interfaces. Experimental measurements and previous theoretical efforts suggest that multiquantal NO vibrational energy relaxation occurs via electron-hole pair excitations in the metal. Here, using a linearized semiclassical approach, we accurately predict the vibrational relaxation of NO from the ν = 3 state for different incident translational energies. We also accurately capture the central role of transient electron transfer from the metal to the molecule in mediating the vibrational relaxation process but fall short of quantitatively predicting the full extent of multiquantum relaxation for high incident vibrational excitations (ν = 16).
从金（111）表面散射的一氧化氮（NO）分子的振动弛豫一直是理解金属 - 分子界面非绝热能量转移研究的重点。实验测量和先前的理论研究表明，多量子NO振动能量弛豫是通过金属中的电子 - 空穴对激发发生的。在这里，我们使用线性化半经典方法，准确预测了不同入射平动能下NO从ν = 3态的振动弛豫。我们还准确捕捉到了从金属到分子的瞬态电子转移在介导振动弛豫过程中的核心作用，但在定量预测高入射振动激发（ν = 16）下多量子弛豫的完整程度方面仍有不足。
