TY - JOUR
T1 - Scaling relationships and theory for vibrational frequencies of adsorbates on transition metal surfaces
AU - Lansford, Joshua L.
AU - Mironenko, Alexander V.
AU - Vlachos, Dionisios G.
N1 - Funding Information:
Financial support from the Defense Advanced Research Project Agency under grant W911NF-15-2-0122 for Lansford and Vlachos is gratefully acknowledged. Support for Mironenko was from the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award no. DE-SC0001004. We also appreciate helpful discussions with Dr. Glen Jenness.
Publisher Copyright:
© 2017 The Author(s).
PY - 2017/12/1
Y1 - 2017/12/1
N2 - Adsorbate vibrational excitations are an important fingerprint of molecule/surface interactions, affecting temperature contributions to the free energy and impacting reaction rate and equilibrium constants. Furthermore, vibrational spectra aid in identifying species and adsorption sites present in experimental studies. Despite their importance, knowledge of how adsorbate frequencies scale across materials is lacking. Here, by combining previously reported experimental data and our own density-functional theory calculations, we reveal linear correlations between vibrational frequencies of adsorbates on transition metal surfaces. Through effective-medium theory, linear muffin-tin orbital theory, and the d-band model, we rationalize the squares of the frequencies to be fundamentally linear in their scaling across transition metal surfaces. We identify the adsorbate-binding energy as a descriptor for certain molecular vibrations and rigorously relate errors in frequencies to errors in adsorption energies. We also discuss the impact of scaling on surface thermochemistry and adsorbate coverage.
AB - Adsorbate vibrational excitations are an important fingerprint of molecule/surface interactions, affecting temperature contributions to the free energy and impacting reaction rate and equilibrium constants. Furthermore, vibrational spectra aid in identifying species and adsorption sites present in experimental studies. Despite their importance, knowledge of how adsorbate frequencies scale across materials is lacking. Here, by combining previously reported experimental data and our own density-functional theory calculations, we reveal linear correlations between vibrational frequencies of adsorbates on transition metal surfaces. Through effective-medium theory, linear muffin-tin orbital theory, and the d-band model, we rationalize the squares of the frequencies to be fundamentally linear in their scaling across transition metal surfaces. We identify the adsorbate-binding energy as a descriptor for certain molecular vibrations and rigorously relate errors in frequencies to errors in adsorption energies. We also discuss the impact of scaling on surface thermochemistry and adsorbate coverage.
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U2 - 10.1038/s41467-017-01983-6
DO - 10.1038/s41467-017-01983-6
M3 - Article
C2 - 29184074
AN - SCOPUS:85036495773
VL - 8
JO - Nature Communications
JF - Nature Communications
SN - 2041-1723
IS - 1
M1 - 1842
ER -