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Dive into the research topics where Ignacio Franco is active.

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Featured researches published by Ignacio Franco.


Journal of the American Chemical Society | 2011

Mechanically activated molecular switch through single-molecule pulling.

Ignacio Franco; Christopher B. George; Gemma C. Solomon; George C. Schatz; Mark A. Ratner

We investigate a prototypical single-molecule switch marrying force spectroscopy and molecular electronics far from the thermodynamic limit. We use molecular dynamics to simulate a conducting atomic force microscope mechanically manipulating a molecule bound to a surface between a folded state and an unfolded state while monitoring the conductance. Both the complexity and the unique phenomenology of single-molecule experiments are evident in this system. As the molecule unfolds/refolds, the average conductance reversibly changes over 3 orders of magnitude; however, throughout the simulation the transmission fluctuates considerably, illustrating the need for statistical sampling in these systems. We predict that emergent single-molecule signatures will still be evident with conductance blinking, correlated with force blinking, being observable in a region of dynamic bistability. Finally, we illustrate some of the structure-function relationships in this system, mapping the dominant interactions in the molecule for mediating charge transport throughout the pulling simulation.


Physical Review Letters | 2007

Robust ultrafast currents in molecular wires through stark shifts

Ignacio Franco; M. Shapiro; Paul Brumer

A novel way to induce ultrafast currents in molecular wires using two incident laser frequencies, omega and 2omega, is demonstrated. The mechanism relies on Stark shifts, instead of near-resonance photon absorption, to transfer population to the excited states and exploits the temporal profile of the field to generate phase-controllable transport. Calculations in a trans- polyacetylene oligomer coupled to metallic leads indicate that the mechanism is highly efficient and robust to ultrafast electronic dephasing processes induced by vibronic couplings.


Journal of Chemical Physics | 2008

Laser-induced currents along molecular wire junctions.

Ignacio Franco; M. Shapiro; Paul Brumer

The treatment of the previous paper is extended to molecular wires. Specifically, the effect of electron-vibrational interactions on the electronic transport induced by femtosecond omega+2omega laser fields along unbiased molecular nanojunctions is investigated. For this, the photoinduced vibronic dynamics of trans-polyacetylene oligomers coupled to macroscopic metallic leads is followed in a mean-field mixed quantum-classical approximation. A reduced description of the dynamics is obtained by introducing projective lead-molecule couplings and deriving an effective Schrodinger equation satisfied by the orbitals in the molecular region. Two possible rectification mechanisms are identified and investigated. The first one relies on near-resonance photon-absorption and is shown to be fragile to the ultrafast electronic decoherence processes introduced by the wires vibrations. The second one employs the dynamic Stark effect and is demonstrated to be highly efficient and robust to electron-vibrational interactions.


Journal of the American Chemical Society | 2011

Tunneling Currents That Increase with Molecular Elongation

Ignacio Franco; Gemma C. Solomon; George C. Schatz; Mark A. Ratner

We present a model molecular system with an unintuitive transport-extension behavior in which the tunneling current increases with forced molecular elongation. The molecule consists of two complementary aromatic units (1,4-anthracenedione and 1,4-anthracenediol) hinged via two ether chains and attached to gold electrodes through thiol-terminated alkenes. The transport properties of the molecule as it is mechanically elongated in a single-molecule pulling setting are computationally investigated using a combination of equilibrium molecular dynamics simulations of the pulling with gDFTB computations of the transport properties in the Landauer limit. Contrary to the usual exponential decay of tunneling currents with increasing molecular length, the simulations indicate that upon elongation electronic transport along the molecule increases 10-fold. The structural origin of this inverted trend in the transport is elucidated via a local current analysis that reveals the dual role played by H-bonds in both stabilizing π-stacking for selected extensions and introducing additional electronic couplings between the complementary aromatic rings that also enhance tunneling currents across the molecule. The simulations illustrate an inverted electromechanical single-molecule switch that is based on a novel class of transport-extension behavior that can be achieved via mechanical manipulation and highlight the remarkable sensitivity of conductance measurements to the molecular conformation.


Journal of Chemical Physics | 2009

Single-molecule pulling and the folding of donor-acceptor oligorotaxanes: Phenomenology and interpretation

Ignacio Franco; George C. Schatz; Mark A. Ratner

The thermodynamic driving force in the folding of a class of oligorotaxanes is elucidated by means of molecular dynamics simulations of equilibrium isometric single-molecule force spectroscopy by atomic force microscopy experiments. The oligorotaxanes consist of cyclobis(paraquat-p-phenylene) rings threaded onto an oligomer of 1,5-dioxynaphthalenes linked by polyethers. The simulations are performed in a high dielectric medium using MM3 as the force field. The resulting force versus extension isotherms show a mechanically unstable region in which the molecule unfolds and, for selected extensions, blinks in the force measurements between a high-force and a low-force regime. From the force versus extension data the molecular potential of mean force is reconstructed using the weighted histogram analysis method and decomposed into energetic and entropic contributions. The simulations indicate that the folding of the oligorotaxanes is energetically favored but entropically penalized, with the energetic contributions overcoming the entropy penalty and effectively driving the folding. In addition, an analogy between the single-molecule folding/unfolding events driven by the atomic force microscope (AFM) tip and the thermodynamic theory of first-order phase transitions is discussed. General conditions (on the molecule and the AFM cantilever) for the emergence of mechanical instabilities and blinks in the force measurements in equilibrium isometric pulling experiments are also presented. In particular, it is shown that the mechanical stability properties observed during the extension are intimately related to the fluctuations in the force measurements.


Journal of Chemical Physics | 2008

Femtosecond dynamics and laser control of charge transport in trans-polyacetylene

Ignacio Franco; M. Shapiro; Paul Brumer

The induction of dc electronic transport in rigid and flexible trans-polyacetylene oligomers according to the omega versus 2omega coherent control scenario is investigated using a quantum-classical mean field approximation. The approach involves running a large ensemble of mixed quantum-classical trajectories under the influence of omega+2omega laser fields and choosing the initial conditions by sampling the ground-state Wigner distribution function for the nuclei. The vibronic couplings are shown to change the mean single-particle spectrum, introduce ultrafast decoherence, and enhance intramolecular vibrational and electronic relaxation. Nevertheless, even in the presence of significant couplings, limited coherent control of the electronic dynamics is still viable, the most promising route involving the use of femtosecond pulses with a duration that is comparable to the electronic dephasing time. The simulations offer a realistic description of the behavior of a simple coherent control scenario in a complex system and provide a detailed account of the femtosecond photoinduced vibronic dynamics of a conjugated polymer.


Journal of Physics B | 2008

Minimum requirements for laser-induced symmetry breaking in quantum and classical mechanics

Ignacio Franco; Paul Brumer

Necessary conditions for generating phase-controllable asymmetry in spatially symmetric systems using lasers are identified and are shown to be identical in quantum and classical mechanics. First, by studying the exact dynamics of harmonic systems in the presence of an arbitrary radiation field, it is demonstrated that anharmonicities in the systems potential are a necessary requirement for phase controllability. Then, by analysing the space-time symmetries of the laser-driven Liouville dynamics for classical and quantum systems, a common set of temporal symmetries for the driving field that need to be violated to induce transport is identified. The conditions apply to continuous wave lasers and to symmetry breaking effects that do not rely on the control of the absolute phase of the field. Known examples of laser fields that can induce transport in symmetric systems are seen to be particular cases of these symmetry constraints.


Journal of Chemical Physics | 2012

Electronic coherence dynamics in trans-polyacetylene oligomers

Ignacio Franco; Paul Brumer

Electronic coherence dynamics in trans-polyacetylene oligomers are considered by explicitly computing the time dependent molecular polarization from the coupled dynamics of electronic and vibrational degrees of freedom in a mean-field mixed quantum-classical approximation. The oligomers are described by the Su-Schrieffer-Heeger Hamiltonian and the effect of decoherence is incorporated by propagating an ensemble of quantum-classical trajectories with initial conditions obtained by sampling the Wigner distribution of the nuclear degrees of freedom. The electronic coherence of superpositions between the ground and excited and between pairs of excited states is examined for chains of different length, and the dynamics is discussed in terms of the nuclear overlap function that appears in the off-diagonal elements of the electronic reduced density matrix. For long oligomers the loss of coherence occurs in tens of femtoseconds. This time scale is determined by the decay of population into other electronic states through vibronic interactions, and is relatively insensitive to the type and class of superposition considered. By contrast, for smaller oligomers the decoherence time scale depends strongly on the initially selected superposition, with superpositions that can decay as fast as 50 fs and as slow as 250 fs. The long-lived superpositions are such that little population is transferred to other electronic states and for which the vibronic dynamics is relatively harmonic.


Physical Review Letters | 2014

Correlated Electron-Nuclear Dynamics with Conditional Wave Functions

Guillermo Albareda; Heiko Appel; Ignacio Franco; Ali Abedi; Angel Rubio

The molecular Schrödinger equation is rewritten in terms of nonunitary equations of motion for the nuclei (or electrons) that depend parametrically on the configuration of an ensemble of generally defined electronic (or nuclear) trajectories. This scheme is exact and does not rely on the tracing out of degrees of freedom. Hence, the use of trajectory-based statistical techniques can be exploited to circumvent the calculation of the computationally demanding Born-Oppenheimer potential-energy surfaces and nonadiabatic coupling elements. The concept of the potential-energy surface is restored by establishing a formal connection with the exact factorization of the full wave function. This connection is used to gain insight from a simplified form of the exact propagation scheme.


Nano Letters | 2014

Molecular Junctions: Can Pulling Influence Optical Controllability?

Shane M. Parker; Manuel Smeu; Ignacio Franco; Mark A. Ratner; Tamar Seideman

We suggest the combination of single molecule pulling and optical control as a way to enhance control over the electron transport characteristics of a molecular junction. We demonstrate using a model junction consisting of biphenyl-dithiol coupled to gold contacts. The junction is pulled while optically manipulating the dihedral angle between the two rings. Quantum dynamics simulations show that molecular pulling enhances the degree of control over the dihedral angle and hence over the transport properties.

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Bing Gu

University of Rochester

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Liping Chen

University of Rochester

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