We use canonical variational theory (CVT) with small-curvature tunneling (SCT) contributions to investigate quantum effects on the H2 diffusion process in the pure-silica zeolite RHO. At low temperature we find an inverse kinetic isotopic sieving effect in that the heavier isotopic species diffuses faster than the lighter one. Three quantum effects contribute to this kinetic isotope effect (KIE). The first one is quantum mechanical tunneling; this - on its own - would lead to a normal kinetic isotopic sieving effect, in which lighter diprotium diffuses faster than dideuterium. The second factor, which we find to dominate in the present case, is zero-point energy (ZPE). Deuterium has a lower ZPE, which leads to a smaller effective barrier for tunneling because the transition state has a larger ZPE than the precursor stable state; this results in an inverse KIE. The third factor, the thermal vibrational energy (computed from the quantized vibrational partition function), also favors a normal KIE, but it is outweighed by the ZPE effect. The vibrations of the zeolite host framework are found to play an important role at low temperatures, and our calculations consider up to 7296 degrees of freedom at the equilibrium structure and the saddle point and up to 221 degrees of freedom along the reaction path. The importance of quantum considerations on the dynamics is elucidated by comparison to a purely classical treatment.
Bibliographical noteFunding Information:
This work was supported in part by a scholarship from China Scholarship Council (201806210213), the National Natural Science Foundation of China (91841301 and 91641127), and as part of the Nanoporous Materials Genome Center by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences under Award DE-FG02-17ER16362.
© 2019 American Chemical Society.