Performance of Made Simple Meta-GGA Functionals with rVV10 Nonlocal Correlation for H₂ + Cu(111), D₂ + Ag(111), H₂ + Au(111), and D₂ + Pt(111)

Abstract

Accurately modeling heterogeneous catalysis requires accurate descriptions of rate-controlling elementary reactions of molecules on metal surfaces, but standard density functionals (DFs) are not accurate enough for this. The problem can be solved with the specific reaction parameter approach to density functional theory (SRP-DFT), but the transferability of SRP DFs among chemically related systems is limited. We combine the MS-PBEl, MS-B86bl, and MS-RPBEl semilocal made simple (MS) meta-generalized gradient approximation (GGA) (mGGA) DFs with rVV10 nonlocal correlation, and we evaluate their performance for the hydrogen (H 2 ) + Cu(111), deuterium (D 2 ) + Ag(111), H 2 + Au(111), and D 2 + Pt(111) gas-surface systems. The three MS mGGA DFs that have been combined with rVV10 nonlocal correlation were not fitted to reproduce particular experiments, nor has the b parameter present in rVV10 been reoptimized. Of the three DFs obtained the MS-PBEl-rVV10 DF yields an excellent description of van der Waals well geometries. The three original MS mGGA DFs gave a highly accurate description of the metals, which was comparable in quality to that obtained with the PBEsol DF. Here, we find that combining the three original MS mGGA DFs with rVV10 nonlocal correlation comes at the cost of a slightly less accurate description of the metal. However, the description of the metal obtained in this way is still better than the descriptions obtained with SRP DFs specifically optimized for individual systems. Using the Born–Oppenheimer static surface (BOSS) model, simulations of molecular beam dissociative chemisorption experiments yield chemical accuracy for the D 2 + Ag(111) and D 2 + Pt(111) systems. A comparison between calculated and measured E 1/2 (ν, J ) parameters describing associative desorption suggests chemical accuracy for the associative desorption of H 2 from Au(111) as well. Our results suggest that ascending Jacob’s ladder to the mGGA rung yields increasingly more accurate results for gas-surface reactions of H 2 (D 2 ) interacting with late transition metals.

SBH17: Benchmark Database of Barrier Heights for Dissociative Chemisorption on Transition Metal Surfaces

“…H 2 + Ag(111) is a highly activated system, for which molecular beam sticking experiments were performed by Hodgson and co-workers . Recently it was shown that the measurements , can be reproduced with chemical accuracy using recently developed made-simple meta-GGA exchange DFs combined with rVV10 nonlocal correlation . Here, we use the barrier height obtained with the functional yielding the best agreement with experiment (MS-PBEl-rVV10) as the reference value for our database (1.082 eV).…”

“…Additionally, the SRP-DF can be considered to be transferable if it can reproduce experimental results for a system it was not fitted to . For example, in some cases, the SRP-DF fitted to reproduce molecular beam dissociation chemisorption experiments for H 2 and D 2 was shown to be transferable among systems in which H 2 interacts with different crystal faces of the same metal. − One downside of the SE SRP-DFT approach to the DC of the molecules on the metal surfaces used so far, in which semilocal exchange DFs are used, is that successful applications of this approach have only been demonstrated to systems for which the difference of the metal work function (W) and the molecule’s electron affinity (EA) is larger than 7 eV. The SRP-DF approach has allowed the construction of chemically accurate barriers for 14 systems , with (W-EA) > 7 eV, as shown in Table and now discussed further below.…”

“…82−85 One downside of the SE SRP-DFT approach to the DC of the molecules on the metal surfaces used so far, in which semilocal exchange DFs are used, is that successful applications of this approach have only been demonstrated to systems for which the difference of the metal work function (W) and the molecule's electron affinity (EA) is larger than 7 eV. The SRP-DF approach has allowed the construction of chemically accurate barriers for 14 systems 10,84 with (W-EA) > 7 eV, as shown in Table 2 and now discussed further below.…”

Optical Constants of Noble Metals at the Nanoscale within the Framework of the Drude Free-Electron Conduction Model: Implications for Liquid Crystal Sensing

“…SAED patterns (panels h−j) illustrate four sets of lattice planes with d spacings of 2.32, 2.04, 1.44, and 1.22 Å that can be attributed to the (111), ( 200), (220), and (311) planes of the face-centered cubic metallic particles. 51 The intrinsic optical properties of metals at the nanoscale dimension have been known since antiquity. However, the scientific understanding of light−matter interactions at the nanoscale has been achieved during the past two centuries.…”

“…Panels e–g represent the corresponding size distribution histograms with a mean diameter of 6 ± 0.5 nm of the copper, silver, and gold nanoparticles, respectively. SAED patterns (panels h–j) illustrate four sets of lattice planes with d spacings of 2.32, 2.04, 1.44, and 1.22 Å that can be attributed to the (111), (200), (220), and (311) planes of the face-centered cubic metallic particles …”