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Performance of the TPSS functional on predicting core level binding energies of main group elements containing molecules: a good choice for molecules adsorbed on metal surfaces

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Here we explored the performance of Hartree-Fock (HF), Perdew-Burke-Ernzerhof (PBE), and Tao-Perdew-Staroverov-Scuseria (TPSS) functionals in predicting core level 1s Binding Energies (BEs) and BE shifts (ΔBEs) for a large set of 68 molecules containing a wide variety of functional groups for main group elements B→F and considering up to 185 core levels. A statistical analysis comparing with X-Ray Photoelectron Spectroscopy (XPS) experiments shows that BEs estimations are very accurate, TPSS exhibiting the best performance. Considering ΔBEs, the three methods yield very similar and excellent results, with mean absolute deviations of ~0.25 eV. When considering relativistic effects, BEs deviations drop approaching experimental values. So, the largest mean percentage deviation is of 0.25% only. Linear trends among experimental and estimated values have been found, gaining offsets with respect ideality. By adding relativistic effects to offsets, HF and TPSS methods underestimate experimental values by solely 0.11 and 0.05 eV, respectively, well within XPS chemical precision. TPSS is posed as an excellent choice for the characterization, by XPS, of molecules on metal solid substrates, given its suitability in describing metal substrates bonds and atomic and/or molecular orbitals.

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PUEYO BELLAFONT, Noèlia, VIÑES SOLANA, Francesc, ILLAS I RIERA, Francesc. Performance of the TPSS functional on predicting core level binding energies of main group elements containing molecules: a good choice for molecules adsorbed on metal surfaces. _Journal of Chemical Theory and Computation_. 2016. Vol. 12, núm. 1, pàgs. 324-331. [consulta: 11 de desembre de 2025]. ISSN: 1549-9618. [Disponible a: https://hdl.handle.net/2445/166167]

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