Switching the conductance of a molecular junction using a proton transfer reaction.

A novel mechanism for switching a molecular junction based on a proton transfer reaction triggered by an external electrostatic field is proposed. As a specific example to demonstrate the feasibility of the mechanism, the tautomers [2,5-(4-hydroxypyridine)] and {2,5-[4(1H)-pyridone]} are considered. Employing a combination of first-principles electronic structure calculations and Landauer transport theory, we show that both tautomers exhibit very different conductance properties and realize the "on" and "off" states of a molecular switch.

Orbital-Symmetry-Dependent Electron Transfer through Molecules Assembled on Metal Substrates.

Femtosecond charge-transfer dynamics in self-assembled monolayers of cyano-terminated ethane-thiolate on gold substrates was investigated with the core hole clock method. By exploiting symmetry selection rules rather than energetic selection, electrons from the nitrogen K-shell are state-selectively excited into the two symmetry-split π* orbitals of the cyano end group with X-ray photons of well-defined polarization. The charge-transfer times from these temporarily occupied orbitals to the metal substrate differ significantly.

Quantum interference and decoherence in single-molecule junctions: how vibrations induce electrical current.

Quantum interference and decoherence in single-molecule junctions is analyzed employing a nonequilibrium Green's function approach. Electrons tunneling through quasidegenerate states of a molecular junction exhibit interference effects. We show that electronic-vibrational coupling, inherent to any molecular junction, strongly quenches such interference effects.

Ultrafast decay of the excited singlet states of thioxanthone by internal conversion and intersystem crossing.

The experimental ultrafast photophysics of thioxanthone in several aprotic organic solvents at room temperature is presented, measured using femtosecond transient absorption together with high-level ab initio CASPT2 calculations of the singlet- and triplet-state manifolds in the gas phase, including computed state minima and conical intersections, transition energies, oscillator strengths, and spin-orbit coupling terms. The initially populated singlet pi pi* state is shown to decay through internal conversion and intersystem crossing processes via intermediate n pi* singlet and triplet states, respectively. Two easily accessible conical intersections explain the favorable internal conversion rates and low fluorescence quantum yields in nonpolar media.

Effects of conjugation length, electron donor and acceptor strengths on two-photon absorption cross sections of asymmetric zinc-porphyrin derivatives.

Exceptionally large two-photon absorption cross sections at the infrared region have been revealed by time-dependent density functional theory calculations for asymmetric charge-transfer conjugated zinc-porphyrin derivatives. The largest two-photon cross section is found to be more than one order of magnitude larger than for the conventional two-photon active organic molecules. The calculations show that the formation of strong charge-transfer states depends on the length of the conjugation bridge between the zinc-porphyrin core and the electron donor/acceptor.

Charge-transfer Zn-porphyrin derivatives with very large two-photon absorption cross sections at 1.3-1.5 microm fundamental wavelengths.

A series of charge-transfer Zn-porphyrin derivatives with large two-photon absorption cross sections at 1.3-1.5 microm fundamental wavelengths are designed using time-dependent hybrid density functional theory.

The permanent dipole moment of gas-phase para-amino benzoic acid revisited.

The permanent dipole moment of para-amino benzoic acid has been calculated at various theoretical levels, including Hartree-Fock, second-order Møller-Plesset perturbation (MP2), coupled cluster singles and doubles (CCSD), and triples corrections CCSD(T), and hybrid density functional theory at B3LYP level. It is found that the B3LYP method fails to provide correct results for the geometry and the permanent dipole moment. These results are significantly improved by MP2 calculations.