An approach to develop chemical intuition for atomistic electron transport calculations using basis set rotations.

Single molecule conductance measurements are often interpreted through computational modeling, but the complexity of these calculations makes it difficult to directly link them to simpler concepts and models. Previous work has attempted to make this connection using maximally localized Wannier functions and symmetry adapted basis sets, but their use can be ambiguous and non-trivial. Starting from a Hamiltonian and overlap matrix written in a hydrogen-like basis set, we demonstrate a simple approach to obtain a new basis set that is chemically more intuitive and allows interpretation in terms of simple concepts and models. By diagonalizing the Hamiltonians corresponding to each atom in the molecule, we obtain a basis set that can be partitioned into pseudo-σ and -π and allows partitioning of the Landuaer-Büttiker transmission as well as create simple Hückel models that reproduce the key features of the full calculation. This method provides a link between complex calculations and simple concepts and models to provide intuition or extract parameters for more complex model systems.

Interference enhanced thermoelectricity in quinoid type structures.

Quantum interference (QI) effects in molecular junctions may be used to obtain large thermoelectric responses. We study the electrical conductance G and the thermoelectric response of a series of molecules featuring a quinoid core using density functional theory, as well as a semi-empirical interacting model Hamiltonian describing the π-system of the molecule which we treat in the GW approximation. Molecules with a quinoid type structure are shown to have two distinct destructive QI features close to the frontier orbital energies. These manifest themselves as two dips in the transmission, that remain separated, even when either electron donating or withdrawing side groups are added. We find that the position of the dips in the transmission and the frontier molecular levels can be chemically controlled by varying the electron donating or withdrawing character of the side groups as well as the conjugation length inside the molecule. This feature results in a very high thermoelectric power factor S(2)G and figure of merit ZT, where S is the Seebeck coefficient, making quinoid type molecules potential candidates for efficient thermoelectric devices.

Bioelectric potentials associated with the growing deer antler.

Bioelectric potentials associated with the developing deer antler throughout its growth cycle can be correlated with the rate of longitudinal bone growth. Electrodes were connected to a high input impediance microvoltmeter, and potentials on the surface of antlers of mature deer were measured during the antler growth cycle. The reference electrode was placed at the base of the antler, while the recording electrode was placed at the antler tip or along the antler shaft. Antler length measurements were made during the growth cycle and longitudinal growth rates were determined. Growth rates and bioelectric potentials were compared for three specified periods during the antler growth cycle. The most negative potential was recorded from the antler tip. Furthermore, electronegativity increased as the rate of growth in length increased and decreased as the rate of growth in length decreased. The potentials reached isopolarity at the end of antler growth.

The effects of continuous direct current on the growth of the antler.

The long-term application of low levels of cathodal direct current to the growing deer antler produced abnormal branching patterns and antlers which grew in atypical directions. The experimental antlers were significantly reduced in length when compared to control antlers.