Communication: Fragment-based Hamiltonian model of electronic charge-excitation gaps and gap closure.

Capturing key electronic properties such as charge excitation gaps within models at or above the atomic scale presents an ongoing challenge to understanding molecular, nanoscale, and condensed phase systems. One strategy is to describe the system in terms of properties of interacting material fragments, but it is unclear how to accomplish this for charge-excitation and charge-transfer phenomena. Hamiltonian models such as the Hubbard model provide formal frameworks for analyzing gap properties but are couched purely in terms of states of electrons, rather than the states of the fragments at the scale of interest. The recently introduced Fragment Hamiltonian (FH) model uses fragments in different charge states as its building blocks, enabling a uniform, quantum-mechanical treatment that captures the charge-excitation gap. These gaps are preserved in terms of inter-fragment charge-transfer hopping integrals T and on-fragment parameters U((FH)). The FH model generalizes the standard Hubbard model (a single intra-band hopping integral t and on-site repulsion U) from quantum states for electrons to quantum states for fragments. We demonstrate that even for simple two-fragment and multi-fragment systems, gap closure is enabled once T exceeds the threshold set by U((FH)), thus providing new insight into the nature of metal-insulator transitions. This result is in contrast to the standard Hubbard model for 1d rings, for which Lieb and Wu proved that gap closure was impossible, regardless of the choices for t and U.

Why are some Interfaces in Materials Stronger than others?

Grain boundaries (GBs) are often the preferred sites for void nucleation in ductile metals. However, it has been observed that all boundaries do not contribute equally to this process. We present a mechanistic rationale for the role of GBs in damage nucleation in copper, along with a quantitative map for predicting preferred void nucleation at GBs based on molecular dynamics simulations in copper. Simulations show a direct correlation between the void nucleation stress and the ability of a grain boundary to plastically deform by emitting dislocations, during shock compression. Plastic response of a GB, affects the development of stress concentrations believed to be responsible for void nucleation by acting as a dissipation mechanism for the applied stress.

Direct transformation of vacancy voids to stacking fault tetrahedra.

Defect accumulation is the principal factor leading to the swelling and embrittlement of materials during irradiation. It is commonly assumed that, once defect clusters nucleate, their structure remains essentially constant while they grow in size. Here, we describe a new mechanism, discovered during accelerated molecular dynamics simulations of vacancy clusters in fcc metals, that involves the direct transformation of a vacancy void to a stacking fault tetrahedron (SFT) through a series of 3D structures. This mechanism is in contrast with the collapse to a 2D Frank loop which then transforms to an SFT. The kinetics of this mechanism are characterized by an extremely large rate prefactor, tens of orders of magnitude larger than is typical of atomic processes in fcc metals.