CO adsorption complexes in zeolites: How does the inclusion of dispersion interactions affect predictions made from DFT calculations? The case of Na-CHA

  • Michael Fischer
  • Montserrat Rodríguez Delgado
  • Carlos Otero Areán
  • Clara Oliver Duran
Regular Article


Density functional theory (DFT) calculations have played a pivotal role in identifying and understanding different coordination modes of carbon monoxide adsorbed in zeolites: Previous studies combining IR spectroscopic measurements and DFT have firmly established that an adsorbed CO molecule can interact either with a single cation (single-site interaction), or with two or more cations simultaneously (dual-site or multiple-site interaction). However, one aspect that has been scarcely addressed so far is the dependence of the DFT equilibrium structures on the choice of the functional. With the ongoing development of DFT, exemplified by the more widespread use of dispersion-corrected DFT, this question becomes increasingly relevant. The present study investigates whether the inclusion of an empirical dispersion correction leads to qualitatively different predictions in comparison with dispersion-uncorrected DFT, taking CO adsorbed in sodium-exchanged chabazite having two different Si/Al ratios (Si/Al = 11:1 and Si/Al = 2:1) as a model system. Equilibrium structures obtained with the PBE functional and with the dispersion-corrected PBE-D functional are compared, revealing a tendency of dispersion-corrected DFT to favour a stronger interaction of CO with dual sites. This is indicated by a short contact between the oxygen atom of the CO molecule (already coordinated through its carbon atom to a primary Na+ cation) and a secondary Na+ cation. In addition to these qualitative findings, the quantitative agreement of calculated adsorption enthalpies and C–O stretching frequencies with experimental values obtained from variable-temperature IR spectroscopy is evaluated. While neither functional is particularly successful in predicting accurate adsorption enthalpies, the range of C–O stretching frequency values delivered by the PBE-D functional shows a better agreement with the experimental measurements.


Density functional theory Dispersion correction Zeolites Adsorption Carbon monoxide VTIR spectroscopy 



M. Fischer acknowledges a postdoctoral fellowship by the German Research Foundation (DFG Grant Fi 1800/1-1), as well as funding by the Central Research Development Fund (CRDF) of the University of Bremen (Funding line 04 – Independent Projects for Post-Docs). M. Fischer is indebted to Dr. Rolf Arvidson and Prof. Andreas Lüttge (Marum) for generous access to the Asgard cluster and further technical support, and to Rob Bell for many insightful discussions, particularly during the initial stages of this project. The Programa Pont “La Caixa” (2014) is gratefully acknowledged for financial support to the work done at the UIB.


  1. 1.
    Areán CO, Nachtigallová D, Nachtigall P, Garrone E, Delgado MR (2007) Thermodynamics of reversible gas adsorption on alkali-metal exchanged zeolites—the interplay of infrared spectroscopy and theoretical calculations. Phys Chem Chem Phys 9:1421–1437. doi: 10.1039/b615535a CrossRefGoogle Scholar
  2. 2.
    Nachtigall P, Delgado MR, Nachtigallova D, Areán CO (2012) The nature of cationic adsorption sites in alkaline zeolites-single, dual and multiple cation sites. Phys Chem Chem Phys 14:1552–1569. doi: 10.1039/c2cp23237e CrossRefGoogle Scholar
  3. 3.
    Van Speybroeck V, Hemelsoet K, Joos L, Waroquier M, Bell RG, Catlow CRA (2015) Advances in theory and their application within the field of zeolite chemistry. Chem Soc Rev. doi: 10.1039/C5CS00029G Google Scholar
  4. 4.
    Ferrari AM, Ugliengo P, Garrone E (1996) Ab initio study of the adducts of carbon monoxide with alkaline cations. J Chem Phys 105:4129–4139. doi: 10.1063/1.472283 CrossRefGoogle Scholar
  5. 5.
    Lupinetti AJ, Fau S, Frenking G, Strauss SH (1997) Theoretical analysis of the bonding between CO and positively charged atoms. J Phys Chem A 101:9551–9559. doi: 10.1021/jp972657l CrossRefGoogle Scholar
  6. 6.
    Broclawik E, Datka J, Gil B, Piskorz W, Kozyra P (2000) The interaction of CO, N2 and NO with Cu cations in ZSM-5: quantum chemical description and IR study. Top Catal 11(12):335–341. doi: 10.1023/A:1027235511555 CrossRefGoogle Scholar
  7. 7.
    Jardillier N, Villagomez EA, Delahay G, Coq B, Berthomieu D (2006) Probing Cu(I)-exchanged zeolite with CO: DFT modeling and experiment. J Phys Chem B 110:16413–16421. doi: 10.1021/jp063190u CrossRefGoogle Scholar
  8. 8.
    Cairon O, Guesmi H (2011) How does CO capture process on microporous NaY zeolites? A FTIR and DFT combined study. Phys Chem Chem Phys 13:11430–11437. doi: 10.1039/c1cp20086k CrossRefGoogle Scholar
  9. 9.
    Nour Z, Berthomieu D (2014) Multiple adsorption of CO on Na-exchanged Y faujasite: a DFT investigation. Mol Simul 40:33–44. doi: 10.1080/08927022.2013.848281 CrossRefGoogle Scholar
  10. 10.
    Bludský O, Šilhan M, Nachtigallová D, Nachtigall P (2003) Calculations of site-specific CO stretching frequencies for copper carbonyls with the “near spectroscopic accuracy”: CO interaction with Cu+/MFI. J Phys Chem A 107:10381–10388. doi: 10.1021/jp036504b CrossRefGoogle Scholar
  11. 11.
    Nachtigallova D, Nachtigall P, Bludsky O (2004) Calculations of the site specific stretching frequencies of CO adsorbed on Li+/ZSM-5. Phys Chem Chem Phys 6:5580–5587. doi: 10.1039/b414296a CrossRefGoogle Scholar
  12. 12.
    Ugliengo P, Busco C, Civalleri B, Zicovich-Wilson CM (2005) Carbon monoxide adsorption on alkali and proton-exchanged chabazite: an ab initio periodic study using the CRYSTAL code. Mol Phys 103:2559–2571. doi: 10.1080/00268970500180865 CrossRefGoogle Scholar
  13. 13.
    Garrone E, Bulánek R, Frolich K, Areán CO, Delgado MR, Palomino GT, Nachtigallová D, Nachtigall P (2006) Single and dual cation sites in zeolites: theoretical calculations and FTIR spectroscopic studies on CO adsorption on K-FER. J Phys Chem B 110:22542–22550. doi: 10.1021/jp0631331 CrossRefGoogle Scholar
  14. 14.
    Nachtigall P, Delgado MR, Frolich K, Bulánek R, Palomino GT, Bauçà CL, Areán CO (2007) Periodic density functional and FTIR spectroscopic studies on CO adsorption on the zeolite Na-FER. Microporous Mesoporous Mater 106:162–173. doi: 10.1016/j.micromeso.2007.02.049 CrossRefGoogle Scholar
  15. 15.
    Areán CO, Delgado MR, Bauçà CL, Vrbka L, Nachtigall P (2007) Carbon monoxide adsorption on low-silica zeolites: from single to dual and to multiple cation sites. Phys Chem Chem Phys 9:4657–4661. doi: 10.1039/b709073k CrossRefGoogle Scholar
  16. 16.
    Areán CO, Delgado MR, Frolich K, Bulánek R, Pulido A, Bibiloni GF, Nachtigall P (2008) Computational and fourier transform infrared spectroscopic studies on carbon monoxide adsorption on the zeolites Na-ZSM-5 and K-ZSM-5: evidence of dual-cation sites. J Phys Chem C 112:4658–4666. doi: 10.1021/jp7109934 CrossRefGoogle Scholar
  17. 17.
    Bulánek R, Voleská I, Ivanova E, Hadjiivanov K, Nachtigall P (2009) Localization and coordination of Mg2+ cations in ferrierite: combined FTIR spectroscopic and computation investigation of CO adsorption complexes. J Phys Chem C 113:11066–11067. doi: 10.1021/jp901575p CrossRefGoogle Scholar
  18. 18.
    Pulido A, Nachtigall P, Delgado MR, Areán CO (2009) Computational and variable-temperature infrared spectroscopic studies on carbon monoxide adsorption on zeolite Ca-A. ChemPhysChem 10:1058–1065. doi: 10.1002/cphc.200800843 CrossRefGoogle Scholar
  19. 19.
    Bulánek R, Drobná H, Nachtigall P, Rubes M, Bludský O (2006) On the site-specificity of polycarbonyl complexes in Cu/zeolites: combined experimental and DFT study. Phys Chem Chem Phys 8:5535–5542. doi: 10.1039/b613805e CrossRefGoogle Scholar
  20. 20.
    Arean CO, Delgado MR, Nachtigall P, Thang HV, Rubeš M, Bulánek R, Chlubná-Eliášová P (2014) Measuring the Brønsted acid strength of zeolites—does it correlate with the O–H frequency shift probed by a weak base? Phys Chem Chem Phys 16:10129–10141. doi: 10.1039/c3cp54738h CrossRefGoogle Scholar
  21. 21.
    Itadani A, Sogawa Y, Oda A, Torigoe H, Ohkubo T, Kuroda Y (2013) Further evidence for the existence of a dual-Cu+ site in MFI working as the efficient site for C2H6 adsorption at room temperature. Langmuir 29:9727–9733. doi: 10.1021/la4018568 CrossRefGoogle Scholar
  22. 22.
    Pham TD, Hudson MR, Brown CM, Lobo RF (2014) Molecular basis for the high CO2 adsorption capacity of chabazite zeolites. ChemSusChem 7:3031–3038. doi: 10.1002/cssc.201402555 CrossRefGoogle Scholar
  23. 23.
    Valenzano L, Civalleri B, Chavan S, Palomino GT, Otero Areán C, Bordiga S (2010) Computational and experimental studies on the adsorption of CO, N2, and CO2 on Mg-MOF-74. J Phys Chem C 114:11185–11191. doi: 10.1021/jp102574f CrossRefGoogle Scholar
  24. 24.
    Valenzano L, Civalleri B, Sillar K, Sauer J (2011) Heats of adsorption of CO and CO2 in metal–organic frameworks: quantum mechanical study of CPO-27-M (M = Mg, Ni, Zn). J Phys Chem C 115:21777–21784. doi: 10.1021/jp205869k CrossRefGoogle Scholar
  25. 25.
    Rubeš M, Grajciar L, Bludský O, Wiersum AD, Llewellyn PL, Nachtigall P (2012) Combined theoretical and experimental investigation of CO adsorption on coordinatively unsaturated sites in CuBTC MOF. ChemPhysChem 13:488–495. doi: 10.1002/cphc.201100602 CrossRefGoogle Scholar
  26. 26.
    Wang H, Zhao L, Xu W, Wang S, Ding Q, Lu X, Guo W (2015) The properties of the bonding between CO and ZIF-8 structures: a density functional theory study. Theor Chem Acc 134:31. doi: 10.1007/s00214-015-1636-4 CrossRefGoogle Scholar
  27. 27.
    Johnson ER, Mackie ID, DiLabio GA (2009) Dispersion interactions in density-functional theory. J Phys Org Chem 22:1127–1135. doi: 10.1002/poc.1606 CrossRefGoogle Scholar
  28. 28.
    Göltl F, Hafner J (2011) Alkane adsorption in Na-exchanged chabazite: the influence of dispersion forces. J Chem Phys 134:064102. doi: 10.1063/1.3549815 CrossRefGoogle Scholar
  29. 29.
    Pulido A, Delgado MR, Bludský O, Rubeš M, Nachtigall P, Areán CO (2009) Combined DFT/CC and IR spectroscopic studies on carbon dioxide adsorption on the zeolite H-FER. Energy Environ Sci 2:1187–1195. doi: 10.1039/b911253g CrossRefGoogle Scholar
  30. 30.
    Zukal A, Pulido A, Gil B, Nachtigall P, Bludský O, Rubes M, Cejka J (2010) Experimental and theoretical determination of adsorption heats of CO2 over alkali metal exchanged ferrierites with different Si/Al ratio. Phys Chem Chem Phys 12:6413–6422. doi: 10.1039/c001950j CrossRefGoogle Scholar
  31. 31.
    Fischer M, Bell RG (2015) A DFT-D study of the interaction of methane, carbon monoxide, and nitrogen with cation-exchanged SAPO-34. Z Kristallogr Cryst Mater 230:311–323. doi: 10.1515/zkri-2014-1802 Google Scholar
  32. 32.
    Zones SI, Van Nordstrand RA (1988) Novel zeolite transformations: the template-mediated conversion of Cubic P zeolite to SSZ-13. Zeolites 8:166–174. doi: 10.1016/S0144-2449(88)80302-6 CrossRefGoogle Scholar
  33. 33.
  34. 34.
    Treacy MMJ, Higgins FM (2001) Collection of simulated XRD powder patterns for zeolites. Elsevier, AmsterdamGoogle Scholar
  35. 35.
    Tsyganenko AA, Storozhev PY, Otero Areán C (2004) IR-spectroscopic study of the binding isomerism of adsorbed molecules. Kinet Catal 45:530–540. doi: 10.1023/B:KICA.0000038081.43384.56 CrossRefGoogle Scholar
  36. 36.
    Areán CO, Manoilova OV, Tsyganenko AA, Palomino GT, Mentruit MP, Geobaldo F, Garrone E (2001) Thermodynamics of hydrogen bonding between CO and the supercage Brønsted acid sites of the H-Y zeolite—studies from variable temperature IR spectrometry. Eur J Inorg Chem 7:1739–1743. doi: 10.1002/1099-0682(200107)2001:7<110.1002/1099-0682(200107)2001:7<1739:AID-EJIC1739 Google Scholar
  37. 37.
    Díaz-Cabañas M-J, Barrett PA, Camblor MA (1998) Synthesis and structure of pure SiO2 chabazite: the SiO2 polymorph with the lowest framework density. Chem Commun. doi: 10.1039/a804800b Google Scholar
  38. 38.
    Fischer M, Bell RG (2013) A dispersion-corrected density-functional theory study of small molecules adsorbed in alkali-exchanged chabazites. Z Kristallogr 228:124–133. doi: 10.1524/zkri.2012.1562 CrossRefGoogle Scholar
  39. 39.
    Momma K, Izumi F (2011) VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J Appl Crystallogr 44:1272–1276. doi: 10.1107/S0021889811038970 CrossRefGoogle Scholar
  40. 40.
    Smith LJ, Eckert H, Cheetham AK (2001) Potassium cation effects on site preferences in the mixed cation zeolite Li, Na-chabazite. Chem Mater 13:385–391. doi: 10.1021/cm0006392 CrossRefGoogle Scholar
  41. 41.
    Caṙtlidge S, Meier WM (1984) Solid state transformations of synthetic CHA-and EAB-type zeolites in the sodium form. Zeolites 4:218–225. doi: 10.1016/0144-2449(84)90027-7 CrossRefGoogle Scholar
  42. 42.
    Smith LJ, Eckert H, Cheetham AK (2000) Site preferences in the mixed cation zeolite, Li, Na-chabazite: a combined solid-state NMR and neutron diffraction study. J Am Chem Soc 122:1700–1708. doi: 10.1021/ja992882b CrossRefGoogle Scholar
  43. 43.
    Shang J, Li G, Singh R, Gu Q, Nairn KM, Bastow TJ, Medhekar N, Doherty CM, Hill AJ, Liu JZ, Webley PA (2012) Discriminative separation of gases by a “molecular trapdoor” mechanism in chabazite zeolites. J Am Chem Soc 134:19246–19253. doi: 10.1021/ja309274y CrossRefGoogle Scholar
  44. 44.
    Clark SJ, Segall MD, Pickard CJ, Hasnip PJ, Probert MIJ, Refson K, Payne MC (2005) First principles methods using CASTEP. Z Kristallogr 220:567–570. doi: 10.1524/zkri.220.5.567.65075 CrossRefGoogle Scholar
  45. 45.
    Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys Rev Lett 77:3865–3868. doi: 10.1103/PhysRevLett.77.3865 CrossRefGoogle Scholar
  46. 46.
    Grimme S (2006) Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J Comput Chem 27:1787–1799. doi: 10.1002/jcc.20495 CrossRefGoogle Scholar
  47. 47.
    Wu Z, Cohen R (2006) More accurate generalized gradient approximation for solids. Phys Rev B 73:235116. doi: 10.1103/PhysRevB.73.235116 CrossRefGoogle Scholar
  48. 48.
    Tkatchenko A, Scheffler M (2009) Accurate molecular van der Waals interactions from ground-state electron density and free-atom reference data. Phys Rev Lett 102:073005. doi: 10.1103/PhysRevLett.102.073005 CrossRefGoogle Scholar
  49. 49.
    Merrick JP, Moran D, Radom L (2007) An evaluation of harmonic vibrational frequency scale factors. J Phys Chem A 111:11683–11700. doi: 10.1021/jp073974n CrossRefGoogle Scholar
  50. 50.
    Civalleri B, Ferrari A, Llunell M, Orlando R, Merawa M, Ugliengo P (2003) Cation selectivity in alkali-exchanged chabazite: an ab initio periodic study. Chem Mater 15:3996–4004. doi: 10.1021/cm0342804 CrossRefGoogle Scholar
  51. 51.
    Hush NS, Williams ML (1974) Carbon monoxide bond length, force constant and infrared intensity variations in strong electric fields: valence-shell calculations, with applications to properties of adsorbed and complexed CO. J Mol Spectrosc 50:349–368. doi: 10.1016/0022-2852(74)90241-0 CrossRefGoogle Scholar
  52. 52.
    Goldman AS, Krogh-Jespersen K (1996) Why do cationic carbon monoxide complexes have high C–O stretching force constants and short C–O bonds ? Electrostatic effects, not σ-bonding. J Am Chem Soc 118:12159–12166. doi: 10.1021/ja960876z CrossRefGoogle Scholar
  53. 53.
    Hadjiivanov KI, Vayssilov GN (2002) Characterization of oxide surfaces and zeolites by carbon monoxide as an IR probe molecule. Adv Catal 47:307–511. doi: 10.1016/S0360-0564(02)47008-3 Google Scholar
  54. 54.
    Otero Areán C, Tsyganenko AA, Escalona Platero E, Garrone E, Zecchina A (1998) Two coordination modes of CO in zeolites: a temperature-dependent equilibrium. Angew Chemie Int Ed 37:3161–3163. doi: 10.1002/(SICI)1521-3773(19981204)37:22<3161:AID-ANIE3161>3.0.CO;2-B CrossRefGoogle Scholar
  55. 55.
    Otero Areán C, Manoilova OV, Turnes Palomino G, Rodríguez Delgado M, Tsyganenko AA, Bonelli B, Garrone E (2002) Variable-temperature infrared spectroscopy: an access to adsorption thermodynamics of weakly interacting systems. Phys Chem Chem Phys 4:5713–5715. doi: 10.1039/b209299a CrossRefGoogle Scholar
  56. 56.
    Garrone E, Otero Areán C (2005) Variable temperature infrared spectroscopy: a convenient tool for studying the thermodynamics of weak solid-gas interactions. Chem Soc Rev 34:846–857. doi: 10.1039/b407049f CrossRefGoogle Scholar
  57. 57.
    Tsyganenko AA, Escalona Platero E, Otero Areán C, Garrone E, Zecchina A (1999) Variable-temperature IR spectroscopic studies of CO adsorbed on Na-ZSM-5 and Na-Y zeolites. Catal Lett 61:187–192. doi: 10.1023/A:1019089309446 CrossRefGoogle Scholar
  58. 58.
    Areán CO, Palomino GT, Tsyganenko AA, Garrone E (2002) Quantum chemical and FTIR spectroscopic studies on the linkage isomerism of carbon monoxide in alkali-metal-exchanged zeolites: a review of current research. Int J Mol Sci 3:764–776. doi: 10.3390/i3070764 CrossRefGoogle Scholar
  59. 59.
    Thang HV, Rubeš M, Bludský O, Nachtigall P (2014) Computational investigation of the Lewis acidity in three-dimensional and corresponding two-dimensional zeolites: UTL vs IPC-1P. J Phys Chem A 118:7526–7534. doi: 10.1021/jp501089n CrossRefGoogle Scholar
  60. 60.
    Fischer M, Bell RG (2014) Cation-exchanged SAPO-34 for adsorption-based hydrocarbon separations: predictions from dispersion-corrected DFT calculations. Phys Chem Chem Phys 16:21062–21072. doi: 10.1039/C4CP01049C CrossRefGoogle Scholar
  61. 61.
    Piccini G, Alessio M, Sauer J, Zhi Y, Liu Y, Kolvenbach R, Jentys A, Lercher JA (2015) Accurate adsorption thermodynamics of small alkanes in zeolites. Ab initio theory and experiment for H-chabazite. J Phys Chem C 119:6128–6137. doi: 10.1021/acs.jpcc.5b01739 CrossRefGoogle Scholar
  62. 62.
    Hermann J, Bludský O (2013) A novel correction scheme for DFT: a combined vdW-DF/CCSD(T) approach. J Chem Phys 139:034115. doi: 10.1063/1.4813826 CrossRefGoogle Scholar
  63. 63.
    Grimme S, Antony J, Ehrlich S, Krieg H (2010) A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys 132:154104. doi: 10.1063/1.3382344 CrossRefGoogle Scholar
  64. 64.
    Göltl F, Sautet P (2014) Modeling the adsorption of short alkanes in the zeolite SSZ-13 using “van der Waals” DFT exchange correlation functionals: understanding the advantages and limitations of such functionals. J Chem Phys 140:154105. doi: 10.1063/1.4871085 CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  • Michael Fischer
    • 1
  • Montserrat Rodríguez Delgado
    • 2
  • Carlos Otero Areán
    • 2
  • Clara Oliver Duran
    • 2
  1. 1.Crystallography Group, Department of GeosciencesUniversity of BremenBremenGermany
  2. 2.Department of ChemistryUniversity of the Balearic IslandsPalma de MallorcaSpain

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