Water adsorption on a copper formate paddlewheel model of CuBTC: A comparative MP2 and DFT study

Accurate Ab Initio Description of Adsorption on Coordinatively Unsaturated Cu2+ and Fe3+ Sites in MOFs

“…24 The accuracy of various exchange-correlation functionals for the description of adsorption in MOFs has already been evaluated; 21,[25][26][27] the relevant studies are briefly discussed below. 24 The accuracy of various exchange-correlation functionals for the description of adsorption in MOFs has already been evaluated; 21,[25][26][27] the relevant studies are briefly discussed below.…”

“…The MP2/CBS results are reported as well, because the MP2 approach is quite often used as a benchmark for the cluster models of the MOFs containing CUSs.19,21,61 The coloring scheme used in The MP2/CBS results are reported as well, because the MP2 approach is quite often used as a benchmark for the cluster models of the MOFs containing CUSs.19,21,61 The coloring scheme used in…”

“…It is also noteworthy that the MP2/CBS level of theory used by Toda et al21 for the evaluation of the Supronowicz et al,27 who employed both PDWL and enlarged cluster models (dicopper tetrabenzenetricarboxylate, Cu 2 BTC 4 ); however, they considered only the B3LYP-D3 functional.The efficiency and reliability of the methods for the description of the interaction of small molecules with CUSs was also evaluated in two studies by Rana et al,26,63 who studied the adsorption of CO 2 in CuBTC and M-DOBDC (M = Mg, Ni, and Co) MOFs. These conclusions are consistent with our results except for the performance of the M05-2X functional, which is caused by a different choice of the reference level of theory (CCSD(T)/CBS vs. MP2/CBS).…”

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

“…Notice that diffuse functions were only considered for the atoms in the hydrocarbon molecule and in the central region of the Na-ETS-10 cluster model, i.e., in the central Na cation (Na2), and in the framework oxygen atoms neighboring the Na2 cation (atoms labeled O1, O2, O5, O6, O7 and Na2 in Figure 1a). 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.…”

Density functional theory meta-GGA + U study of water incorporation in the metal-organic framework material Cu-BTC

“…A recent X-ray powder diffraction refinement, [21] on the other hand, shows evidence for 2.3 bound water molecules per Cu atom, in three different partially occupied binding sites, although it was not possible to determine the hydrogen positions for these water molecules. Previous electronic structure calculations and molecular simulations have generally investigated the structure of H 2 O in Cu-BTC only up to one H 2 O per Cu ion, [22][23][24][25] in which case one water molecule binds to each Cu position, with the water oxygen atom (O W ) closest to the Cu. In this work, we use density functional theory at the "meta-GGA + U" level to investigate the structure of water absorption in Cu-BTC up to 3.5 H 2 O per Cu.…”