Anharmonicity in a double hydrogen transfer reaction studied in a single porphycene molecule on a Cu(110) surface

S. Liu, D. Baugh, K. Motobayashi, X. Zhao, S. V. Levchenko, S. Gawinkowski, J. Waluk, L. Grill, M. Persson, T. Kumagai

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Abstract

Anharmonicity plays a crucial role in hydrogen transfer reactions in hydrogen-bonding systems, which leads to a peculiar spectral line shape of the hydrogen stretching mode as well as highly complex intra/intermolecular vibrational energy relaxation. Single-molecule study with a well-defined model is necessary to elucidate a fundamental mechanism. Recent low-temperature scanning tunnelling microscopy (STM) experiments revealed that the cis ↔ cis tautomerization in a single porphycene molecule on Cu(110) at 5 K can be induced by vibrational excitation via an inelastic electron tunnelling process and the N-H(D) stretching mode couples with the tautomerization coordinate [Kumagai et al. Phys. Rev. Lett. 2013, 111, 246101]. Here we discuss a pronounced anharmonicity of the N-H stretching mode observed in the STM action spectra and the conductance spectra. Density functional theory calculations find a strong intermode coupling of the N-H stretching with an in-plane bending mode within porphycene on Cu(110).

Original languageEnglish
Pages (from-to)12112-12119
Number of pages8
JournalPhysical Chemistry Chemical Physics
Volume20
Issue number17
DOIs
Publication statusPublished - 2018
Externally publishedYes

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