Justin P. Bergfield

Thermoelectric Signatures of Coherent Transport in Single-Molecule Heterojunctions

An exact expression for the heat current in an interacting nanostructure is derived and used to calculate the thermoelectric response of three representative single-molecule junctions formed from isoprene, 1,3-benzenedithiol, and [18]-annulene. Dramatic enhancements of the thermopower S and Lorenz number L are predicted when the junction is tuned across a node in the transmission function, with universal maximum values S(max) = (pi/3(1/2))(k(B)/e) and L(max) = (7pi(2)/5)(k(B)(2)/e(2)). The effect of a finite minimum transmission probability due, e.g., to incoherent processes or additional nonresonant channels, is also considered.

Many-body theory of electronic transport in single-molecule heterojunctions

A many-body theory of molecular junction transport based on nonequilibrium Greens functions is developed, which treats coherent quantum effects and Coulomb interactions on an equal footing. The central quantity of the many-body theory is the Coulomb self-energy matrixC of the junction. �C is evaluated exactly in the sequential tunneling limit, and the correction due to finite tunnel- ing width is evaluated self-consistently using a conserving approximation based on diagrammatic perturbation theory on the Keldysh contour. Our approach reproduces the key features of both the Coulomb blockade and coherent transport regimes simultaneously in a single unified transport theory. As a first application of our theory, we have calculated the thermoelectric power and dif- ferential conductance spectrum of a benzenedithiol-gold junction using a semi-empirical �-electron Hamiltonian that accurately describes the full spectrum of electronic excitations of the molecule up to 8-10eV.

Novel quantum interference effects in transport through molecular radicals.

We investigate electronic transport through molecular radicals and predict a correlation-induced transmission node arising from destructive interference between transport contributions from different charge states of the molecule. This quantum interference effect has no single-particle analog and cannot be described by effective single-particle theories. Large errors in the thermoelectric properties and nonlinear current-voltage response of molecular radical junctions are introduced when the complementary wave and particle aspects of the electron are not properly treated. A method to accurately calculate the low-energy transport through a radical-based junction using an Anderson model is given.

Accuracy of density functionals for molecular electronics: The Anderson junction

The exact ground-state exchange-correlation functional of Kohn-Sham density functional theory yields the exact transmission through an Anderson junction at zero bias and temperature. The exact impurity charge susceptibility is used to construct the exact exchange-correlation potential. We analyze the successes and limitations of various types of approximations, including smooth and discontinuous functionals of the occupation, as well as symmetry-broken approaches.

The number of transmission channels through a single-molecule junction.

We calculate transmission eigenvalue distributions for Pt-benzene-Pt and Pt-butadiene-Pt junctions using realistic state-of-the-art many-body techniques. An effective field theory of interacting π-electrons is used to include screening and van der Waals interactions with the metal electrodes. We find that the number of dominant transmission channels in a molecular junction is equal to the degeneracy of the molecular orbital closest to the metal Fermi level.

Local temperature of out-of-equilibrium quantum electron systems

We show how the local temperature of out-of-equilibrium, quantum electron systems can be consistently defined with the help of an external voltage and temperature probe. We determine sufficient conditions under which the temperature measured by the probe (i) is independent of details of the system-probe coupling, (ii) is equal to the temperature obtained from an independent current-noise measurement, (iii) satisfies the transitivity condition expressed by the zeroth law of thermodynamics, and (iv) is consistent with Carnots theorem. This local temperature therefore characterizes the system in the common sense of equilibrium thermodynamics, but remains well defined even in out-of-equilibrium situations with no local equilibrium.

Harnessing Quantum Interference in Molecular Dielectric Materials.

We investigate the relationship between dielectric response and charge transport in molecule-based materials operating in the quantum coherent regime. We find that quantum interference affects these observables differently, for instance, allowing current passing through certain materials to be reduced by orders of magnitude without affecting dielectric behavior (or band gap). As an example, we utilize ab initio electronic structure theory to calculate conductance and dielectric constants of cross-conjugated anthraquinone (AQ)-based and linearly conjugated anthracene (AC)-based materials. In spite of having nearly equal fundamental gaps, electrode bonding configurations, and molecular dimensions, we find a ∼1.7 order of magnitude (∼50-fold) reduction in the conductance of the AQ-based material relative to the AC-based material, a value in close agreement with recent measurements, while the calculated dielectric constants of both materials are nearly identical. From these findings, we propose two molecular materials in which quantum interference is used to reduce leakage currents across a ∼25 Å monolayer gap with dielectric constants larger than 4.5.

Coherent destruction of Coulomb blockade peaks in molecular junctions

Coherent electronic transport in single-molecule junctions is investigated in the Coulomb blockade regime. Both the transmission phase and probability are calculated for junctions with various contact symmetries. A dramatic suppression of the Coulomb blockade peaks is predicted for junctions where multiple atomic orbitals of the molecule couple to a single electrode although the charging steps are unaffected.

Probing Maxwell's demon with a nanoscale thermometer.

A precise definition for a quantum electron thermometer is given, as an electron reservoir coupled locally (e.g., by tunneling) to a sample, and brought into electrical and thermal equilibrium with it. A realistic model of a scanning thermal microscope with atomic resolution is then developed, including the effect of thermal coupling of the probe to the ambient environment. We show that the temperatures of individual atomic orbitals or bonds in a conjugated molecule with a temperature gradient across it exhibit quantum oscillations, whose origin can be traced to a realization of Maxwells demon at the single-molecule level. These oscillations may be understood in terms of the rules of covalence describing bonding in π-electron systems. Fouriers law of heat conduction is recovered as the resolution of the temperature probe is reduced, indicating that the macroscopic law emerges as a consequence of coarse graining.

Effective field theory of interacting π electrons

We develop a \pi-electron effective field theory (\pi-EFT) wherein the two-body Hamiltonian for a \pi-electron system is expressed in terms of three effective parameters: the \pi-orbital quadrupole moment, the on-site repulsion, and a dielectric constant. As a first application of this \pi-EFT, we develop a model of screening in molecular junctions based on image multipole moments, and use this to investigate the reduction of the HOMO-LUMO gap of benzene. Beyond this, we also use \pi-EFT to calculate the differential conductance spectrum of the prototypical benzenedithiol-Au single-molecule junction and the \pi-electron contribution to the van der Waals interaction between benzene and a metallic electrode.