The chemisorption energy is an integral aspect of surface chemistry,central to numerous fields such as catalysis,corrosion,and nanotechnology.Electronic-structure-based methods such as the Newns-Anderson model are the...The chemisorption energy is an integral aspect of surface chemistry,central to numerous fields such as catalysis,corrosion,and nanotechnology.Electronic-structure-based methods such as the Newns-Anderson model are therefore of great importance in guiding the engineering of material surfaces with optimal properties.However,existing methods are inadequate for interpreting complex,multi-metallic systems.Herein,we introduce a physics-based chemisorption model for alloyed transition metal surfaces employing primarily metal d-band properties that accounts for perturbations in both the substrate and adsorbate electronic states upon interaction.Importantly,we show that adsorbate-induced changes in the adsorption site interact with its chemical environment leading to a second-order response in chemisorption energy with the d-filling of the neighboring atoms.We demonstrate the robustness of the model on a wide range of transition metal alloys with O,N,CH,and Li adsorbates yielding a mean absolute error of 0.13 eV versus density functional theory reference chemisorption energies.展开更多
基金J.H.S.gratefully acknowledge funding via the Knut and Alice Wallenberg foundation(grant no.2019.0586)We thank Dr.Johannes Voss,Dr.Karun Kumar Rao and Dr.Benjamin Comer for fruitful discussions and acknowledge computational support from the National Energy Research Scientific Computing Center(computer time allocation m2997),a DOE Office of Science User Facility supported by the Office of Science of the U.S.Department of Energy under Contract No.DE-AC02-05CH11231.
文摘The chemisorption energy is an integral aspect of surface chemistry,central to numerous fields such as catalysis,corrosion,and nanotechnology.Electronic-structure-based methods such as the Newns-Anderson model are therefore of great importance in guiding the engineering of material surfaces with optimal properties.However,existing methods are inadequate for interpreting complex,multi-metallic systems.Herein,we introduce a physics-based chemisorption model for alloyed transition metal surfaces employing primarily metal d-band properties that accounts for perturbations in both the substrate and adsorbate electronic states upon interaction.Importantly,we show that adsorbate-induced changes in the adsorption site interact with its chemical environment leading to a second-order response in chemisorption energy with the d-filling of the neighboring atoms.We demonstrate the robustness of the model on a wide range of transition metal alloys with O,N,CH,and Li adsorbates yielding a mean absolute error of 0.13 eV versus density functional theory reference chemisorption energies.
