表面键收缩的证据.pdf

Evidence for surface bond contraction Chang Q. Sun,* S. Li, and B. K. Tay School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 Reddy and Reddy1 misinterpreted our bond order-length-strength (BOLS) correlation mechanism2,3 and then mis-derived that if the BOLS correlation holds, the lattice parameter of the ZnMnTe nanosolid should be equal to that of the bulk with large surface strain rather than the ~8 % contraction (for the 12.5 nm sized particle) as they measured using X-ray diffraction. Clarification of this mis-derivative is necessary. The BOLS correlation based on the earlier conventions4,5,6 of atomic-CN – atomic-radius correlation was proposed for the anomalous behavior of surface and nanosolid, which states that: 1. The termination of the lattice periodicity in the surface normal has two effects. One is to create a potential barrier at the surface and the other is to reduce the coordination number (CN) of the surface atom. The potential barrier confines electrons or holes moving inside the solid but the confinement does no matter with the lattice constant. 2. The CN-imperfection of an atom results in spontaneousl contraction of the remaining bonds of the lower-coordinated atom 4-6 associated with magnitude increase of the binding energy or enhancement of the bond strength. The BOLS correlation contributes not only to the cohesive energy (Ecoh, single bond energy multiplies the atomic CN) of the lower-coordinated surface atom but also to the energy density in the relaxed region. The former determines the thermaldynamic behaviour of the atom and the solid such as critical temperature for phase transition and liquidation; 7 the latter provides purturbation to the Hamiltonian that determines the entire band structure such as the badn gap, core level posi