Calculating the frequencies and intensities of strongly anharmonic modes of adsorbates on surfaces : a low-cost but accurate computational approach
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We present a new method for calculating the frequencies and intensities of the vibrational modes of adsorbates on surfaces. Our method is based on density functional perturbation theory (DFPT) and provides accurate estimates of the vibrational intensities even when the vibrations are strongly anharmonic. Furthermore, it does so at a negligible additional computation cost compared to conventional DFPT calculation. We illustrate our method by calculating the vibrational spectra of three example systems — ethylidyne on Rh(111), benzene on Rh(111) coadsorbed with CO, and terephthalic acid (TPA) on Cu(100) — and comparing them to experimental measurements performed using High-Resolution Electron Energy Loss Spectroscopy (HREELS). We find excellent agreement between our predictions and the experimentally measured frequencies and intensities in all three cases.
Garrido Torres , J A , Goetze , J P , Grillo , F , Richardson , N V , Früchtl , H A , Hooley , C A & Schaub , R 2019 , ' Calculating the frequencies and intensities of strongly anharmonic modes of adsorbates on surfaces : a low-cost but accurate computational approach ' , Physical Review. B, Condensed matter and materials physics , vol. 100 , no. 3 , 035433 . https://doi.org/10.1103/PhysRevB.100.035433
Physical Review. B, Condensed matter and materials physics
Copyright © 2019 American Physical Society. This work has been made available online in accordance with the publisher’s policies. This is the author created accepted version manuscript following peer review and as such may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1103/PhysRevB.100.035433
DescriptionFunding: Scottish Funding Council (through EaStCHEM and SRD-Grant HR07003) and from EPSRC (PhD studentship for JAGT, EP/M506631/1).
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