The adsorption of N2 and CO in Na X-zeolites has been studied for different framework structures and extraframework cation distributions. To this aim, the cation-molecule system modeling one site has been embedded in a set of external point charges which simulate the zeolite environment of the site and has been treated quantum chemically, using a method based on density functional theory. This procedure has been applied to the 64 cationic sites accessible for adsorption in a crystal unit cell of an ideal X-zeolite with a Si/Al ratio equal to 1. These calculations have shown that only a few cations are favorable for initial adsorption and that those cations are always of type III(III ′). Their efficiency depends both on the framework geometry and on their location in the supercages. The analysis of the quantum chemical results in terms of a classical description involving electrostatic and induction interaction energies with the framework has led to the conclusion that the direction of the electric field vector created by the zeolite in the supercages is an important factor determining the zeolite adsorption properties. Zeolites are aluminosilicate materials that are widely used for size and shape catalysis, hydrocarbon conversion, and sorbing processes. Their physicochemical properties are based on the ability of these open crystalline structures to enclose charged and neutral species within cavities. Their properties are thus strongly related to the structure of the framework and also to the distribution among cages and channels of the cations that are associated with the Al centers. Indeed, those extraframework cations are the active sites for adsorption processes, whereas their neighboring oxygens are involved in base catalysis. Adsorption and desorption studies of small probe molecules like N2 and CO are used to provide information about cations and basic sites. Those experiments show that the adsorption of molecules within the cages varies with the number and nature of occupied cationic sites. 1-3 However, there is presently no real understanding of how adsorption properties of zeolites depend on the cation distribution. The major difficulty encountered in the study of such a correlation arises from the incomplete information provided by experimental structure determinations about cationic sites. First, very few structures are known for low-silica zeolites, i.e. for those including a large number of cations. 4 Moreover, the studies concerned with zeolites containing a single type of cations are even more scarce, due to the difficulty of full cationic exchange. Crystal and powder structure determinations provide positions for the cations associated with the probabilities of occupying the various sites, which, very often, do not sum up to the total number of cations. Cation positions vary also with their chemical nature and with the extent of dehydration. Lithium cations are hardly detectable by X-ray diffraction, and sodium cations may not be well differentiated from water molecules. Finally, experimental conditions of preparation and dehydration may induce differences in the solids, leading to different structures and thus different adsorption properties. For all these reasons, we think that modeling may be an appropriate tool to analyze the relations between adsorption properties and zeolite structures. Although a large variety of modeling techniques have already been used for the prediction and analysis of zeolite structures and properties, only a very few studies have been devoted to systems including cations other than protons. During the last decade, the main effort has been devoted to H-zeolites, mainly due to their widespread applications in acid catalysis. 5-7 Only recently have some dynamical studies of Na and Ca A-zeolite, 8-10 Na Y-zeolite, 11 and Na and K offretite 12 proposed detailed structures including cation positions. In recent papers, we have shown that the nature of the cation and its location in the framework are essential factors for N2 and O2 adsorption. 13,14 In these studies, it was shown that short-range interactions between incoming molecules and
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