Hydrogen/deuterium adsorption and absorption properties on and in palladium using a combined plane wave and localized basis set method

Abstract

Detailed information on the H/D isotope effects for adsorption on the surface and absorption in the bulk is important for understanding the nuclear quantum effect. To achieve this, we developed a new theoretical approach, namely, the combined plane wave and localized basis set (CPLB) method. By using the multicomponent quantum chemical method, which takes into account the quantum effect of a proton or deuteron, with the localized part of the CPLB method, direct analysis of the H/D isotope effect about adsorption and absorption is carried out. In this study, we performed a theoretical investigation of the H/D isotope effects for adsorption on a Pd(111) surface and absorption in bulk Pd. We clearly showed an H/D isotope effect on geometry during adsorption and absorption. Our developed CPLB approach is a powerful tool for analyzing the quantum nature of H/D in surface, bulk, and inhomogeneous systems.

Theoretical study of the H/D isotope effect of CH4/CD4 adsorption on a Rh(111) surface using a combined plane wave and localized basis sets method

“…These results indicate that the geometrical changes due to D substitution for H were opposite in the r(C/Rh) and covalent r(C-X) cases and H/ D atomic adsorption on the Pd(111) surface. 21 The difference in r(C/Rh) is similar to the Ubbelohde effect observed in typical hydrogen-bonded systems. 35,36 Hence, the C/Rh interaction was considered to be different from H/D atomic adsorption and essentially the same as the typical hydrogen-bonded systems.…”

“…We have already reported the efficiency of the CPLB method in analysing the H/D isotope effects of H/D atomic adsorption on the Pd(111) surface. 21 In this study, we calculated the CH 4 /CD 4 adsorption on the Rh(111) surface, which is a model of C 6 H 12 /C 6 H 12 adsorption on Rh(111) surface experimentally, 10 using the CPLB method to analyse and understand the geometrical and energetic changes induced by the H/D isotope effect.…”

“…We have already reported the efficiency of the CPLB method in analysing the H/D isotope effects of H/D atomic adsorption on the Pd(111) surface. 21 …”

Adsorption and Absorption Energies of Hydrogen with Palladium

“… d The classical energy required to move an H or D atom from the surface to the bulk is ϵ sb = 0.46 ± 0.01 eV. e Combined plane wave and localized basis set method (CPLB) from ref ( 38 ) predicts −0.292 eV. See the Discussion Section.…”

“… e Combined plane wave and localized basis set method (CPLB) from ref ( 38 ) predicts −0.292 eV. See the Discussion Section.…”