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Fig. 1. View of the cluster model (a) cut from the periodic structure of Na-ETS-10 (polymorph B from Ref. [2]) shown in (b). The spheres in (a) represent atoms fully optimizec while sticks represent frozen atoms at their periodic positions. Note that terminal Si atoms were replaced by H in (a). Color code is: Bluish-green for Ti, yellow for Si, red for O violet for Na and white for H. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

Figure 1 View of the cluster model (a) cut from the periodic structure of Na-ETS-10 (polymorph B from Ref. [2]) shown in (b). The spheres in (a) represent atoms fully optimizec while sticks represent frozen atoms at their periodic positions. Note that terminal Si atoms were replaced by H in (a). Color code is: Bluish-green for Ti, yellow for Si, red for O violet for Na and white for H. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

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* Atomic labeling in Fig. 1 with x = 1 or 2, y = 1-4 or 6-9, z= 1, 2, 6 or 7; distances in A and angles in degrees. > Range of results calculated in this work with different functionals. Comparison of selected DFT geometrical parameters for the bare Na-ETS-10 cluster model with the corresponding experimental and ONIOM(DFT:MM) data taken from the literature.
* Atomic labeling in Fig. 1 with x = 1 or 2, y = 1-4 or 6-9, z= 1, 2, 6 or 7; distances in A and angles in degrees. > Range of results calculated in this work with different functionals. Comparison of selected DFT geometrical parameters for the bare Na-ETS-10 cluster model with the corresponding experimental and ONIOM(DFT:MM) data taken from the literature.
* Available experimental enthalpies of interaction are: —21.4 kJ/mol (Toth model, Ref. [17]), —21.0 kJ/mol (unilan model, Ref. [17]), —20.8 kJ/mol (virial three con- stants model, Ref. [17]), —22.9 kJ/mol (virial three constants model, Ref. [58]), —23.3 kJ/mol (Toth model, Ref. [22]). Energies and enthalpies in parentheses do not include BSSE corrections. Optimized sorbate to cation distances (d(Na*---C), A), interaction energies (AE, k]J/ mol) and interaction enthalpies at T= 298.15 K (AH?9°-!5%, kJ/mol) calculated at the DFT/6-31G(d,p) level of theory for CH, adsorption at the 12-MR of Na-ETS-10.*
* Available experimental enthalpies of interaction are: —21.4 kJ/mol (Toth model, Ref. [17]), —21.0 kJ/mol (unilan model, Ref. [17]), —20.8 kJ/mol (virial three con- stants model, Ref. [17]), —22.9 kJ/mol (virial three constants model, Ref. [58]), —23.3 kJ/mol (Toth model, Ref. [22]). Energies and enthalpies in parentheses do not include BSSE corrections. Optimized sorbate to cation distances (d(Na*---C), A), interaction energies (AE, k]J/ mol) and interaction enthalpies at T= 298.15 K (AH?9°-!5%, kJ/mol) calculated at the DFT/6-31G(d,p) level of theory for CH, adsorption at the 12-MR of Na-ETS-10.*
Fig. 2. Configurations optimized with the MO6-L/6-31++G(d,p) approach and the counterpoise method for CHy, interacting with Na-ETS-10, viewed along directions parall (a) and normal (b) to the -Ti-O-Ti- chain. Dashed lines show the distances between the sodium cation and each individual atom of the sorbate. Color code is the same as | Fig. 1, plus grey for Carbon. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Fig. 2. Configurations optimized with the MO6-L/6-31++G(d,p) approach and the counterpoise method for CHy, interacting with Na-ETS-10, viewed along directions parall (a) and normal (b) to the -Ti-O-Ti- chain. Dashed lines show the distances between the sodium cation and each individual atom of the sorbate. Color code is the same as | Fig. 1, plus grey for Carbon. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Fig. 3. Configurations optimized with the MO06-L/6-31++G(d,p) approach and the counterpoise method for N interacting with Na-ETS-10, viewed along directions parallel (a and normal (b) to the -Ti-O-Ti- chain. Dashed lines show the distances between the sodium cation and each individual atom of the sorbate. Color code is the same as i! Fig. 1, plus blue for Nitrogen. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Fig. 3. Configurations optimized with the MO06-L/6-31++G(d,p) approach and the counterpoise method for N interacting with Na-ETS-10, viewed along directions parallel (a and normal (b) to the -Ti-O-Ti- chain. Dashed lines show the distances between the sodium cation and each individual atom of the sorbate. Color code is the same as i! Fig. 1, plus blue for Nitrogen. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Fig. 4. Configurations optimized with the MO06-L/6-31++G(d,p) approach and the counterpoise method for H2 interacting with Na-ETS-10, viewed along directions parallel (a) and normal (b) to the -Ti-O-Ti- chain. Dashed lines show the distances between the sodium cation and each individual atom of the sorbate. Color code is the same as in Fig. 1. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Fig. 4. Configurations optimized with the MO06-L/6-31++G(d,p) approach and the counterpoise method for H2 interacting with Na-ETS-10, viewed along directions parallel (a) and normal (b) to the -Ti-O-Ti- chain. Dashed lines show the distances between the sodium cation and each individual atom of the sorbate. Color code is the same as in Fig. 1. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
* Distances in the bare model are also provided for comparison purposes. > Nearest neighbor distances, except for methane where the Na2-C distance i given. Sodium to adsorbate and sodium to framework oxygens distances (A) optimized at the M06-L/6-31++G(d,p) level of theory using BSSE corrections.*
* Distances in the bare model are also provided for comparison purposes. > Nearest neighbor distances, except for methane where the Na2-C distance i given. Sodium to adsorbate and sodium to framework oxygens distances (A) optimized at the M06-L/6-31++G(d,p) level of theory using BSSE corrections.*
Comparison between the experimental isosteric heats of adsorption (AH'*°**"*) and the calculated energies (AE) or enthalpies of interaction (AH' *) at temperatures T= 0 K or 298.15 K. All values in kJ/mol.* * Data in parenthesis were calculated with the M06-L/6-31G(d,p) approach while the remaining values were obtained at the M06-L/6-31++G(d,p) level of theo: interaction energies and enthalpies include BSSE corrections. > Air adsorption.
Comparison between the experimental isosteric heats of adsorption (AH'*°**"*) and the calculated energies (AE) or enthalpies of interaction (AH' *) at temperatures T= 0 K or 298.15 K. All values in kJ/mol.* * Data in parenthesis were calculated with the M06-L/6-31G(d,p) approach while the remaining values were obtained at the M06-L/6-31++G(d,p) level of theo: interaction energies and enthalpies include BSSE corrections. > Air adsorption.
Fig. 5. Configurations optimized with the M06-L/6-31++G(d,p) approach and the counterpoise method for CO2 interacting with Na-ETS-10, viewed along directions parall (a) and normal (b) to the -Ti-O-Ti- chain. Dashed lines show the distances between the sodium cation and each individual atom of the sorbate. Color code is the same as Fig. 1, plus grey for Carbon. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Fig. 5. Configurations optimized with the M06-L/6-31++G(d,p) approach and the counterpoise method for CO2 interacting with Na-ETS-10, viewed along directions parall (a) and normal (b) to the -Ti-O-Ti- chain. Dashed lines show the distances between the sodium cation and each individual atom of the sorbate. Color code is the same as Fig. 1, plus grey for Carbon. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Fig. 6. Configurations optimized with the MO6-L/6-31++G(d,p) approach and the counterpoise method for H2O interacting with Na-ETS-10, viewed along directions parallel (a) and normal (b) to the -Ti-O-Ti- chain. Dashed lines show the distances between the sodium cation and each individual atom of the sorbate. Color code is the same as in Fig. 1. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Fig. 6. Configurations optimized with the MO6-L/6-31++G(d,p) approach and the counterpoise method for H2O interacting with Na-ETS-10, viewed along directions parallel (a) and normal (b) to the -Ti-O-Ti- chain. Dashed lines show the distances between the sodium cation and each individual atom of the sorbate. Color code is the same as in Fig. 1. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Comparison of relevant calculated and experimental vibrational frequencies (cm~') for the isolated gas molecules. 4 MO6-L/6-31++G(d,p) level of theory; scale factor for vibrations above 1000 cm“! is 0.949 while vibrations below are unscaled. > Fermi resonance. Table 5
Comparison of relevant calculated and experimental vibrational frequencies (cm~') for the isolated gas molecules. 4 MO6-L/6-31++G(d,p) level of theory; scale factor for vibrations above 1000 cm“! is 0.949 while vibrations below are unscaled. > Fermi resonance. Table 5
Comparison of relevant calculated and experimental vibrational frequencies (cm~') for different adsorbed molecules in Na-ETS-10 Table 6
Comparison of relevant calculated and experimental vibrational frequencies (cm~') for different adsorbed molecules in Na-ETS-10 Table 6
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