NO Vibrational Energy Transfer on a Metal Surface: Still a Challenge to First-Principles Theory

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• 作者：Bastian C. Kr眉ger ; Nils Bartels ; Christof Bartels ; Alexander Kandratsenka ; John C. Tully ; Alec M. Wodtke ; Tim Sch盲fer
• 刊名：Journal of Physical Chemistry C
• 出版年：2015
• 出版时间：February 12, 2015
• 年：2015
• 卷：119
• 期：6
• 页码：3268-3272
• 全文大小：267K
• ISSN：1932-7455

文摘

During a collision of highly vibrationally excited NO with a Au(111) surface, the molecule can lose a large fraction of its vibrational energy into electronic excitation of the metal. This process violates the Born鈥揙ppenheimer approximation and represents a major challenge to theories of molecule鈥搒urface interaction. Two ab initio approaches to this problem, one using independent electron surface hopping (IESH) and the other electronic friction, previously reported good agreement with the limited available data on multiquantum vibrational relaxation; however, at that time only experiments for NO(v_i = 15) at an incidence translational energy of E_i = 0.05 eV were available. In this work, we report a comparison of recently reported experiments characterizing the multiquantum vibrational relaxation of NO on Au(111) for a wider range of incidence translational and vibrational energies to IESH and molecular dynamics with electronic friction (MDEF) calculations for these conditions. Both theories fail to explain the large amount of vibrational energy transferred from NO to the solid.