Improved CO Adsorption Energies, Site Preferences, and Surface Formation Energies from a Meta-Generalized Gradient Approximation Exchange–Correlation Functional, M06-L

Abstract

A notorious failing of approximate exchange-correlation functionals when applied to problems involving catalysis has been the inability of most local functionals to predict the correct adsorption site for CO on metal surfaces or to simultaneously predict accurate surface formation energies and adsorption energies for transition metals. By adding the kinetic energy density τ to the density functional, the revTPSS density functional was shown recently to achieve a balanced description of surface energies and adsorption energies. Here, we show that the older M06-L density functional, also containing τ, provides improved surface formation energies and CO adsorption energies over revTPSS for five transition metals and correctly predicted the on-top/hollow site adsorption preferences for four of the five metals, which was not achieved by most other local functionals. Because M06-L was entirely designed on the basis of atomic and molecular energies, its very good performance is a confirmation of the reasonableness of its functional form. Two GGA functionals with an expansion in the reduced gradient that is correct through second order, namely, SOGGA and SOGGA11, were also tested and found to produce the best surface formation energies of all tested GGA functionals, although they significantly overestimate the adsorption energies.

Accounting for van der Waals interactions between adsorbates and surfaces in density functional theory based calculations: selected examples

“…We have confirmed the adequacy of these approaches in the past for two difficult systems, e.g. CO adsorption on MgO(100) 58 and CO and NO adsorption on Nidoped MgO(100), 59 which are also corroborated by the quite encouraging results from recent works concerning the interaction of CO with the (111) surfaces of Rh, Pt, Cu, Ag and Pd 106 or the interaction of benzene, pyridine, thymine and cytosine with Au (111), 107 where the M06-L method and a periodic model approach were used. Another very hot topic where DFT approaches including van der Waals corrections are being used is in the study of the interaction of graphene with adsorbates 70,77,[97][98][99]108 or with a substrate.…”

A density functional theory study on the interaction of paraffins, olefins, and acetylenes with Na-ETS-10

“…The M06-L functional is used in this work since in a recent comparative study on the performance of nine different DFT functionals to calculate the interaction enthalpy of methane with a cluster model of Na-ETS-10, the M06-L approach was found to provide the best results [21].Besides,the M06-L approach together with a cluster model was found to provide very accurate energetic, vibrational and structural information for some other difficult systems such as i) adsorption of CO on MgO(001) [30], ii) the adsorption of CO and NO on Ni-doped MgO(001) [31], and iii) the interaction of water with open metal sites of CuBTC [32]. Very encouragingly, recent works concerning the interaction of CO with the (111) surfaces of Rh, Pt, Cu, Ag and Pd [33] or the interaction of benzene, pyridine, thymine and cytosine with Au(111) [34]showed that the M06-L method is suitable for treating dispersion dominated interactionsof adsorbateswith metallic surfaces [35].The M06-L approach was also effectively employed to predict reaction energies in organometallic systems [36][37][38] and the benchmark study on the interaction of hydrocarbons and smaller gases with several zeolite clusters byZhao and Truhlar [39]shows that the M06 family of functionals is well suited to study this kind of systems.Additionally, in our very recent work on the interaction of five atmospheric gases with Na-ETS-10 [21], calculated enthalpic data for methane, nitrogen and, at some extent, carbon dioxide, and calculated vibrational data for methane, nitrogen, hydrogen, carbon dioxide and water were found to be in very satisfactory agreement with experimental isosteric heats [40,41] and infrared results [42][43][44][45], respectively. The same 2Ti cluster model used in Ref.…”

Ultranonlocality and accurate band gaps from a meta-generalized gradient approximation

“…In solid-state physics, the prediction of the fundamental (band) gap is an intrinsic limitation of explicit density-dependent semilocal functionals [7,8]. In material science, the proper description of charge localization and charge distributions between subsystems is a major challenge [9,10] that affects many problems, e.g., surface adsorption [11,12]. In molecular physics and chemistry, missing field-counteracting terms have serious, detrimental consequences for the calculation of polarizabilities, hyperpolarizabilities, and charge transfer [13][14][15].…”