The nature of the low energy band of the Fenna-Matthews-Olson complex: vibronic signatures

Based entirely upon actual experimental observations on electron-phonon coupling, we develop a theoretical framework to show that the lowest energy band of the Fenna-Matthews-Olson complex exhibits observable features due to the quantum nature of the vibrational manifolds present in its chromophores. The study of linear spectra provides us with the basis to understand the dynamical features arising from the vibronic structure in nonlinear spectra in a progressive fashion, starting from a microscopic model to finally performing an inhomogeneous average. We show that the discreteness of the vibronic structure can be witnessed by probing the diagonal peaks of the nonlinear spectra by means of a relative phase shift in the waiting time resolved signal. Moreover, we demonstrate that the photon-echo and non-rephasing paths are sensitive to different harmonics in the vibrational manifold when static disorder is taken into account. Supported by analytical and numerical calculations, we show that non-diagonal resonances in the 2D spectra in the waiting time, further capture the discreteness of vibrations through a modulation of the amplitude without any effect in the signal intrinsic frequency. This fact generates a signal that is highly sensitive to correlations in the static disorder of the excitonic energy albeit protected against dephasing due to inhomogeneities of the vibrational ensemble.     

A guide to Sonogashira cross-coupling reactions: the influence of substituents in aryl bromides, acetylenes, and phosphines

The conversion-time data for 168 different Pd/Cu-catalyzed Sonogashira cross-coupling reactions of five arylacetylenes (phenylacetylene; 1-ethynyl-2-ethylbenzene; 1-ethynyl-2,4,6-R(3)-benzene (R = Me, Et, i-Pr)) and Me(3)SiCCH with seven aryl bromides (three 2-R-bromobenzenes (R = Me, Et, i-Pr); 2,6-Me(2)-bromobenzene and three 2,4,6-R(3)-bromobenzenes (R = Me, Et, i-Pr)) with four different phosphines (P-t-Bu(3), t-Bu(2)PCy, t-BuPCy(2), PCy(3)) were determined using quantitative gas chromatography. The stereoelectronic properties of the substituents in the aryl bromides, acetylenes, and phosphines were correlated with the performance in Sonogashira reactions. It was found that the nature of the most active Pd/PR(3) complex for a Sonogashira transformation is primarily determined by the steric bulk of the acetylene; ideal catalysts are: Pd/P-t-Bu(3) or Pd/t-Bu(2)PCy for sterically undemanding phenylacetylene, Pd/t-BuPCy(2) for 2- and 2,6-substituted arylacetylenes or Me(3)SiCCH and Pd/PCy(3) for extremely bulky acetylenes and aryl bromides. Electron-rich and sterically demanding aryl bromides with substituents in the 2- or the 2,6-position require larger amounts of catalyst than 4-substituted aryl bromides. The synthesis of tolanes with bulky groups at one of the two aryl rings is best done by placing the steric bulk at the arylacetylene, which is also the best place for electron-withdrawing substituents.     

Robust creation of entanglement between ions in spatially separate cavities

We present a protocol that allows the generation of a maximally entangled state between individual atoms held in spatially separate cavities. Assuming perfect detectors and neglecting spontaneous emission from the atoms, the resulting idealized scheme is deterministic. Under more realistic conditions, when the atom-cavity interaction departs from the strong coupling regime, and considering imperfect detectors, we show that the scheme is robust against experimental inefficiencies and yields probabilistic entanglement of very high fidelity.     

Light-shift-induced quantum gates for ions in thermal motion

An effective interaction between trapped ions in thermal motion can be generated by illuminating them simultaneously with a single laser resonant with the ionic carrier frequency. The ac Stark shift induces simultaneous "virtual" two-phonon transitions via several motional modes. Within a certain laser intensity range these transitions can interfere constructively, resulting in a relatively fast, heating-resistant two-qubit logic gate.     

Towards quantum entanglement in nanoelectromechanical devices

We study arrays of mechanical oscillators in the quantum domain and demonstrate how the motions of distant oscillators can be entangled without the need for control of individual oscillators and without a direct interaction between them. These oscillators are thought of as being members of an array of nanoelectromechanical resonators with a voltage being applicable between neighboring resonators. Sudden nonadiabatic switching of the interaction results in a squeezing of the states of the mechanical oscillators, leading to an entanglement transport in chains of mechanical oscillators. We discuss spatial dimensions, Q factors, temperatures and decoherence sources in some detail, and find a distinct robustness of the entanglement in the canonical coordinates in such a scheme. We also briefly discuss the challenging aspect of detection of the generated entanglement.