Nonlinearly coupled localized plasmon resonances: Resonant second-harmonic generation

The efficient resonant nonlinear coupling between localized surface plasmon modes is demonstrated in a simple and intuitive way using boundary integral formulation and utilizing second-order optical nonlinearity. The nonlinearity is derived from the hydrodynamic description of electron plasma and originates from the presence of material interfaces in the case of small metal particles. The coupling between fundamental and second-harmonic modes is shown to be symmetry selective and proportional to the spatial overlap between polarization dipole density of the second-harmonic mode and the square of the polarization charge density of the fundamental mode. Particles with high geometrical symmetry will convert a far-field illumination into dark nonradiating second-harmonic modes, such as quadrupoles. Effective second-harmonic susceptibilities are proportional to the surface-to-volume ratio of a particle, emphasizing the nanoscale enhancement of the effect.

Dynamics of excess electronic charge in aliphatic ionic liquids containing the bis(trifluoromethylsulfonyl)amide anion

In a recent article (J. Am. Chem. Soc. 2011, 133, 20186) we investigated the initial spatial distribution of dry excess electrons in a series of room-temperature ionic liquids (RTILs). Perhaps unexpectedly, we found that in some alkylammonium-based systems the excess negative charge resided on anions and not on the positive cations. Following on these results, in the current paper we describe the time evolution of an excess electronic charge introduced in alkylammonium- and pyrrolidinium-based ionic liquids coupled with the bis(trifluoromethylsulfonyl)amide ([TfN]) anion. We find that on a 50 fs time scale an initially delocalized excess electron localizes on a single [TfN] anion which begins a fragmentation process. Low-energy transitions have a very different physical origin on the several femtoseconds time scale when compared to what occurs on the picosecond time scale. At time zero, these are intraband transitions of the excess electron. However after 40 fs when the excess electronic charge localizes on a single anion, these transitions disappear, and the spectrum is dominated by electron-transfer transitions between the fragments of the doubly charged breaking anion. © 2013 American Chemical Society.

Spatially-resolved mapping of history-dependent coupled electrochemical and electronical behaviors of electroresistive NiO

Bias-induced oxygen ion dynamics underpins a broad spectrum of electroresistive and memristive phenomena in oxide materials. Although widely studied by device-level and local voltage-current spectroscopies, the relationship between electroresistive phenomena, local electrochemical behaviors, and microstructures remains elusive. Here, the interplay between history-dependent electronic transport and electrochemical phenomena in a NiO single crystalline thin film with a number of well-defined defect types is explored on the nanometer scale using an atomic force microscopy-based technique. A variety of electrochemically-active regions were observed and spatially resolved relationship between the electronic and electrochemical phenomena was revealed. The regions with pronounced electroresistive activity were further correlated with defects identified by scanning transmission electron microscopy. Using fully coupled mechanical-electrochemical modeling, we illustrate that the spatial distribution of strain plays an important role in electrochemical and electroresistive phenomena. These studies illustrate an approach for simultaneous mapping of the electronic and ionic transport on a single defective structure level such as dislocations or interfaces, and pave the way for creating libraries of defect-specific electrochemical responses.

Non-Markovian qubit dynamics in a circuit-QED setup

We consider a circuit-QED setup that allows the induction and control of non-Markovian dynamics of a qubit. Non-Markovianity is enforced over the qubit by means of its direct coupling to a bosonic mode which is controllably coupled to another qubit-mode system. We show that this configuration can be achieved in a circuit-QED setup consisting of two initially independent superconducting circuits, each formed by one charge qubit and one transmission-line resonator, which are put in interaction by coupling the resonators to a current-biased Josephson junction. We solve this problem exactly and then proceed with a thorough investigation of the emergent non-Markovianity in the dynamics of the qubits. Our study might serve the context for the first experimental assessment of non-Markovianity in a multielement solid-state device.

Ultrafast charge-transfer in organic photovoltaic interfaces: geometrical and functionalization effects

Understanding the microscopic mechanisms of electronic excitation in organic photovoltaic cells is a challenging problem in the design of efficient devices capable of performing sunlight harvesting. Here we develop and apply an ab initio approach based on time-dependent density functional theory and Ehrenfest dynamics to investigate photoinduced charge transfer in small organic molecules. Our calculations include mixed quantum–classical dynamics with ions moving classically and electrons quantum mechanically, where no experimental external parameter other than the material geometry is required. We show that the behavior of photocarriers in zinc phthalocyanine (ZnPc) and C60 systems, an effective prototype system for organic solar cells, is sensitive to the atomic orientation of the donor and the acceptor units as well as the functionalization of covalent molecules at the interface. In particular, configurations with the ZnPc molecules facing on C60 facilitate charge transfer between substrate and molecules that occurs within 200 fs. In contrast, configurations where ZnPc is tilted above C60 present extremely low carrier injection efficiency even at longer times as an effect of the larger interfacial potential level offset and higher energetic barrier between the donor and acceptor molecules. An enhancement of charge injection into C60 at shorter times is observed as binding groups connect ZnPc and C60 in a dyad system. Our results demonstrate a promising way of designing and controlling photoinduced charge transfer on the atomic level in organic devices that would lead to efficient carrier separation and maximize device performance.