Tully J C
Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107, USA.
Annu Rev Phys Chem. 2000;51:153-78. doi: 10.1146/annurev.physchem.51.1.153.
Theoretical aspects of dynamical processes at metal surfaces are reviewed. Experimental challenges to theory are presented and progress toward meeting these challenges is appraised. Topics include adsorbate vibrational energy flow, inelastic molecule-surface scattering, adsorption, transient mobility, dissociation, desorption, photochemistry, and electron-induced chemistry at metal surfaces. Experimental examples cited illustrate the richness of dynamical phenomena to be understood and the necessity of developing multidimensional, beyond Born-Oppenheimer, formulations of adsorbate dynamics. Classical mechanical and quantum mechanical treatments of dynamics are contrasted. The importance of including phonon and electron-hole pair dissipation in theories of adsorbate dynamics is emphasized, and strategies for doing this in classical and quantum treatments are presented.
本文综述了金属表面动力学过程的理论方面。介绍了理论面临的实验挑战，并评估了应对这些挑战所取得的进展。主题包括吸附质振动能流、非弹性分子-表面散射、吸附、瞬态迁移率、解离、脱附、光化学以及金属表面的电子诱导化学。所引用的实验示例说明了有待理解的动力学现象的丰富性，以及发展超越玻恩-奥本海默近似的多维吸附质动力学公式的必要性。对比了动力学的经典力学和量子力学处理方法。强调了在吸附质动力学理论中纳入声子和电子-空穴对耗散的重要性，并提出了在经典和量子处理中实现这一点的策略。
