Density Functional Theory Study of NO Adsorbed in A-Zeolite

Density functional theory was employed to investigate the adsorption site and hyperfine interactions of nitric oxide adsorbed in Na-LTA (previous name NaA) zeolite. Three different cluster models of increasing complexity were used to represent the zeolite network: (1) a six-membered ring terminated by hydrogen atoms with one sodium ion above the ring, (2) as model 1 with the addition of three sodium ions located at the centers of three imagined four-membered rings adjacent to the six-membered ring, and (3) as model 2 with the addition of the three four-membered rings adjacent to the six-membered ring. Calculations on the largest system (model 3) showed very good agreement with measured electronic Zeeman interaction couplings, 14N hyperfine coupling tensors, and 23Na hyperfine and nuclear quadruple coupling tensors of the S = 1/2 Na+···N−O adsorption complex when the position of the sodium ion was relaxed. The optimized geometry of the complex agreed nicely with that estimated experimentally, except for the Na−N distance, where the present results indicate that the distance deduced from previous ENDOR experiments may be underestimated by as much as 0.5 Å.