Isomeric effects tuning the electron transport in carotenoid derivatives: from ohmic to rectifier behavior.

Single-molecules have been widely investigated in the last decades due to their promises as devices in molecular electronics. One of the advantages in the use of natural compounds in molecular electronics is the economy of material and molecular synthesis, which makes the process both cheaper and self-sustaining. Although many studies have considered electronic transport in single molecules, there are few studies associated with isomeric effects in biologically appealing systems. In the present work, we have studied ballistic electron transport in two isomeric forms of a retinol molecule: 11-cis and all-trans-retinol. The molecules were connected between two Au(111) electrodes and calculations were performed with the NEGF-DFT methodology. Current-voltage, differential conductance, and rectification curves were obtained and compared for two structures. While 11-cis-retinol shows a more symmetrical current-voltage curve, all-trans-retinol acts as molecular diode for low applied voltages. Our results suggest that a simple isomeric effect modulates the molecular device from nanowires to diodes with potential applications as field-effect transistors.

Investigation of electronic transport under mechanical strain in a molecular junction composed of a polyyne bridge connected to SWCNT electrodes.

In the present work we propose a novel treatment to investigate ballistic electron transport under mechanical strain in a 1-D molecular bridge composed of alternating simple and triple bonds (polyyne) connected between two Single-Wall Carbon Nanotube (SWCNT) electrodes. Calculations with the DFT-NEGF methodology were performed in order to analyze this system at low values of mechanical strain (compression and distension) and at equilibrium length in the presence of bias voltages applied along the longitudinal direction. The results show that, while the mechanical strain displaces the energy levels and changes the band gap in the nanotube caps, the applied bias breaks the degeneracy in the nanotube cap states and defines the electrical conductance along the system. The analysis of the PDOS suggests that the main contribution to the electrical current comes from the superposition of the nanotube cap states, which is in agreement with the transmission calculation, and this device can be employed as a transistor observed in the I-V curve.

Single-molecular diodes based on opioid derivatives.

We propose an efficient single-molecule rectifier based on a derivative of opioid. Electron transport properties are investigated within the non-equilibrium Green's function formalism combined with density functional theory. The analysis of the current-voltage characteristics indicates obvious diode-like behavior. While heroin presents rectification coefficient R>1, indicating preferential electronic current from electron-donating to electron-withdrawing, 3 and 6-acetylmorphine and morphine exhibit contrary behavior, R<1. Our calculations indicate that the simple inclusion of acetyl groups modulate a range of devices, which varies from simple rectifying to resonant-tunneling diodes. In particular, the rectification rations for heroin diodes show microampere electron current with a maximum of rectification (R=9.1) at very low bias voltage of ∼0.6 V and (R=14.3)∼1.8 V with resistance varying between 0.4 and 1.5 M Ω. Once most of the current single-molecule diodes usually rectifies in nanoampere, are not stable over 1.0 V and present electrical resistance around 10 M. Molecular devices based on opioid derivatives are promising in molecular electronics.

The UV-vis absorption spectrum of the flavonol quercetin in methanolic solution: A theoretical investigation.

The UV-vis absorption spectrum of the solvated quercetin molecule in methanol was investigated theoretically by means of an elegant type of QM/MM scheme better known as sequential Monte Carlo/quantum mechanics (S-MC/QM) methodology. A set of 125 uncorrelated Monte Carlo molecular liquid structures were properly selected through the autocorrelation function of the energy in order to be used in the quantum mechanical calculations. These molecular liquid structures were obtained by means of the radial and minimum distance distribution functions. A detailed account of the pattern of hydrogen bond structures obtained in this study is also available. The computed results obtained here were directly compared with the available experimental data in order to validate our theoretical model and through this comparison a very good conformity between theoretical and available experimental results was found.

Theoretical and experimental investigation of the second hyperpolarizabilities of methyl orange.

We describe experimental and theoretical studies of the third-order nonlinear optical coefficients of methyl orange solutions under different pH conditions. A combination of semiempirical and ab initio methods was adopted to investigate the most stable geometrical structures possible for this molecule. The experimental data obtained using the Z-scan technique for the third-order nonlinear optical properties of this compound has allowed the determination of the nonlinear refractive index and nonlinear absorption coefficient under picosecond excitation in the visible (532 nm) spectral region. From those experimental results, the second hyperpolarizability of methyl orange was inferred both for acidic and alkaline solutions. Comparison of these values to the results predicted by semiempirical methods suggests that even at low pH, when the probability of cis-trans isomerization is increased, the trans conformation of the methyl orange molecule should dominate the nonlinear spectra of this compound. The theoretical results were used as an auxiliary tool to identify possible trends on the nonlinear properties changes as a function of the distinct molecular conformations adopted by the methyl orange molecule under different pH conditions.