Tunneling through superlattices: the effect of anisotropy and kinematic coupling.

The tunneling of carriers in stratified superlattice systems is analyzed in terms of the constituent effective mass tensor. The focus is on the effects on the tunneling which are caused by the side regions of an intervening barrier. Depending on the covalency and work function in the constituent layers of a superlattice, it is concluded that the kinematics in the regions on either side determined by the effective carrier mass and its interference with the band offset at heterojunctions leads to either a constructive or a destructive effect on the tunneling current. As an example, Si(1-x)Ge(x)/Si and Al(x)Ga(1-x)As/GaAs superlattices are demonstrated to reduce the tunneling current at certain fractional thicknesses and stoichiometries of the constituent slabs without affecting the lateral mobility. The findings show, in general, how manipulation of the carrier's effective mass tensor through stoichiometric/structural modulation of the heterostructure may be used to control the tunneling current through a given potential barrier, given that the characteristic de Broglie wavelength exceeds all the constituent dimensions, thus offering a method complementary to high-k technologies.

Thermodynamics of catalytic formation of dimethyl ether from methanol in acidic zeolites.

We present a theoretical study of the formation of the first intermediate, dimethyl ether, in the methanol to gasoline conversion within the framework of an ab initio molecular dynamics approach. The study is performed under conditions that closely resemble the reaction conditions in the zeolite catalyst including the full topology of the framework. The use of the method of thermodynamic integration allows us to extract the free-energy profile along the reaction coordinate. We find that the entropic contribution qualitatively alters the free-energy profile relative to the total energy profile. Different transition states are found from the internal and free energy profiles. The entropy contribution varies significantly along the reaction coordinate and is responsible for stabilizing the products and for lowering the energy barrier. The hugely inhomogeneous variation of the entropy can be understood in terms of elementary processes that take place during the chemical reaction. Our simulations provide new insights into the complex nature of this chemical reaction.