Over-Stoichiometric Metastabilization of Cation-Disordered Rock Salts.

Cation-disordered rock salts (DRXs) are well known for their potential to realize the goal of achieving scalable Ni- and Co-free high-energy-density Li-ion batteries. Unlike in most cathode materials, the disordered cation distribution may lead to more factors that control the electrochemistry of DRXs. An important variable that is not emphasized by research community is regarding whether a DRX exists in a more thermodynamically stable form or a more metastable form. Moreover, within the scope of metastable DRXs, over-stoichiometric DRXs, which allow relaxation of the site balance constraint of a rock salt structure, are particularly underexplored. In this work, these findings are reported in locating a generally applicable approach to "metastabilize" thermodynamically stable Mn-based DRXs to metastable ones by introducing Li over-stoichiometry. The over-stoichiometric metastabilization greatly stimulates more redox activities, enables better reversibility of Li deintercalation/intercalation, and changes the energy storage mechanism. The metastabilized DRXs can be transformed back to the thermodynamically stable form, which also reverts the electrochemical properties, further contrasting the two categories of DRXs. This work enriches the structural and compositional space of DRX families and adds new pathways for rationally tuning the properties of DRX cathodes.

Hierarchical Self-Assembly of Carbon Dots into High-Aspect-Ratio Nanowires.

We report a spontaneous and hierarchical self-assembly mechanism of carbon dots prepared from citric acid and urea into nanowire structures with large aspect ratios (>50). Scattering-type scanning near-field optical microscopy (s-SNOM) with broadly tunable mid-IR excitation was used to interrogate details of the self-assembly process by generating nanoscopic chemical maps of local wire morphology and composition. s-SNOM images capture the evolution of wire formation and the complex interplay between different chemical constituents directing assembly over the nano- to microscopic length scales. We propose that residual citrate promotes tautomerization of melamine surface functionalities to produce supramolecular shape synthons comprised of melamine-cyanurate adducts capable of forming long-range and highly directional hydrogen-bonding networks. This intrinsic, heterogeneity-driven self-assembly mechanism reflects synergistic combinations of high chemical specificity and long-range cooperativity that may be harnessed to reproducibly fabricate functional structures on arbitrary surfaces.

Molecular Optomechanics Induced Hybrid Properties in Soft Materials Filled Plasmonic Nanocavities.

The optomechanical interaction between nanocavity plasmons and molecular vibrations can result in interfacial phenomena that can be tailored for sensing and photocatalytic applications. Here, we report for the first time that plasmon-vibration interaction can induce laser-plasmon detuning dependent plasmon resonance linewidth broadening, indicating energy transfer from the plasmon field to collective vibrational modes. The linewidth broadening accompanied by the large enhancement of the Raman scattering signal is observed as the laser-plasmon blue-detuning approaches the CH vibrational frequency of the molecular systems integrated in gold nanorod-on-mirror nanocavities. The experimental observations can be explained based on the molecular optomechanics theory that predicts dynamical backaction amplification of the vibrational modes and high sensitivity of Raman scattering when the plasmon resonance overlaps with the Raman emission frequency. The results presented here suggest that molecular optomechanics coupling may be manipulated for creating hybrid properties based on interactions between molecular oscillators and nanocavity electromagnetic optical modes.

Extracting Electronic Transition Bands of Adsorbates from Molecule-Plasmon Excitation Coupling.

The coupling between molecular electronic and particle plasmon excitations can result in various intriguing outcomes depending on how strongly or weakly the excitations couple to compete with their respective decay rates. In this work, using methylene blue and thionine dyes as model systems, we show that the electronic absorption band of resonant adsorbates can be determined with submonolayer sensitivity from the weak molecule-plasmon excitation coupling that results in the attenuation on the plasmonic absorption band. The extracted spectra are strongly similar to the absorption spectra of the corresponding molecules in solution, apart from the expected spectral red-shift and broadening. Interestingly, the adsorption isotherms determined on the basis of the magnitude of the attenuation correlate linearly with that determined from the adsorbate-induced plasmon resonance red-shift. The results demonstrate that in the weak coupling regimes the plasmon modes can be considered as an environment that supplies energy to and takes energy from the adsorbates.

Observation of Intersubband Polaritons in a Single Nanoantenna Using Nano-FTIR Spectroscopy.

Strong coupling of an intersubband (ISB) electron transition in quantum wells to a subwavelength plasmonic nanoantenna can give rise to intriguing quantum phenomena, such as ISB polariton condensation, and enable practical devices including low threshold lasers. However, experimental observation of ISB polaritons in an isolated subwavelength system has not yet been reported. Here, we use scanning probe near-field microscopy and Fourier-transform infrared (FTIR) spectroscopy to detect formation of ISB polariton states in a single nanoantenna. We excite the nanoantenna by a broadband IR pulse and spectrally analyze evanescent fields on the nanoantenna surface. We observe the distinctive splitting of the nanoantenna resonance peak into two polariton modes and two π-phase steps corresponding to each of the modes. We map ISB polariton dispersion using a set of nanoantennae of different sizes. This nano-FTIR spectroscopy approach opens doors for investigations of ISB polariton physics in the single subwavelength nanoantenna regime.

Adsorption of methylene blue and its N-demethylated derivatives on the (111) face of coinage metals: The importance of dispersion interactions.

The adsorption of methylene blue and its N-demethylated derivatives on the (111) surface of three coinage metals is investigated using density functional theory with and without the inclusion of dispersion interactions. It is shown that the adsorption of these dye molecules on the metal surfaces can be largely classified as physisorption as the adsorption energy is dominated by dispersion interactions. While the molecules are found to adsorb on Au and Ag parallel to the surface with molecular geometries basically unaltered, the adsorption on Cu(111) features a butterfly configuration, accompanied by the largest adsorption energies among the three metal surfaces. The significant covalent character on Cu(111) is analyzed from the perspective of electronic structure.

Active Mediation of Plasmon Enhanced Localized Exciton Generation, Carrier Diffusion and Enhanced Photon Emission.

Understanding the enhancement of charge carrier generation and their diffusion is imperative for improving the efficiency of optoelectronic devices particularly infrared photodetectors that are less developed than their visible counterpart. Here, using gold nanorods as model plasmonic systems, InAs quantum dots (QDs) embedded in an InGaAs quantum well as an emitter, and GaAs as an active mediator of surface plasmons for enhancing carrier generation and photon emission, the distance dependence of energy transfer and carrier diffusion have been investigated both experimentally and theoretically. Analysis of the QD emission enhancement as a function of distance reveals a Förster radius of 3.85 ± 0.15 nm, a near-field decay length of 4.8 ± 0.1 nm and an effective carrier diffusion length of 64.0 ± 3.0 nm. Theoretical study of the temporal-evolution of the electron-hole occupation number of the excited states of the QDs indicates that the emission enhancement trend is determined by the carrier diffusion and capture rates.

Surface Ligand-Mediated Plasmon-Driven Photochemical Reactions.

Contrary to the general expectation that surface ligands reduce the reactivity of surfaces by blocking the active sites, we present experimental evidence that surface ligands can in fact increase reactivity and induce important reaction pathways in plasmon-driven surface photochemistry. The remarkable effect of surface ligands is demonstrated by comparing the photochemistry of p-aminothiophenol (PATP) on resonant plasmonic gold nanorods (AuNRs) in the presence of citrate, hexadecyltrimethylammonium bromide (CTAB), and no surface ligands under visible light irradiation. The use of AuNRs with citrate and no surface ligand results in the usual azo-coupling reaction. In contrast, CTAB-coated AuNRs oxidize PATP primarily to p-nitrothiophenol (PNTP). Strong correlation has been observed between the N-O and Au-Br vibration band intensities, suggesting that CTAB influences the reaction pathway through the Br- counterions that can minimize the electron-hole recombination rate by reacting with the hole and hence increasing the concentration of hot electrons that drive the oxidation reaction.

Large-Area Semiconducting Graphene Nanomesh Tailored by Interferometric Lithography.

Graphene nanostructures are attracting a great deal of interest because of newly emerging properties originating from quantum confinement effects. We report on using interferometric lithography to fabricate uniform, chip-scale, semiconducting graphene nanomesh (GNM) with sub-10 nm neck widths (smallest edge-to-edge distance between two nanoholes). This approach is based on fast, low-cost, and high-yield lithographic technologies and demonstrates the feasibility of cost-effective development of large-scale semiconducting graphene sheets and devices. The GNM is estimated to have a room temperature energy bandgap of ~30 meV. Raman studies showed that the G band of the GNM experiences a blue shift and broadening compared to pristine graphene, a change which was attributed to quantum confinement and localization effects. A single-layer GNM field effect transistor exhibited promising drive current of ~3.9 µA/µm and ON/OFF current ratios of ~35 at room temperature. The ON/OFF current ratio of the GNM-device displayed distinct temperature dependence with about 24-fold enhancement at 77 K.

Probe-sample optical interaction: size and wavelength dependence in localized plasmon near-field imaging.

The probe-sample optical interaction in apertureless near-field optical microscopy is studied at 633 nm and 808 nm excitation wavelengths using gold nanodisks as model systems. The near-field distributions of the dipolar and quadrupolar surface plasmon modes have been mapped successfully using metal coated probes with different polarization combinations of excitation and detection except when the incident and the scattered light polarizations are chosen to be parallel to the probe axis. For the parallel polarization of the incident and the scattered light, the pattern of the near-field distribution differs from the inherent plasmon mode structures of the sample, depending sensitively on the sample size and excitation energy. For a given excitation energy, the near-field amplitude shifts from one pole to the other as the sample size increases, having nearly equal amplitude at the two poles when the plasmon resonance peak spectrally overlaps with the excitation energy.

Metallic adhesion layer induced plasmon damping and molecular linker as a nondamping alternative.

Drastic chemical interface plasmon damping is induced by the ultrathin (∼2 nm) titanium (Ti) adhesion layer; alternatively, molecular adhesion is implemented for lithographic fabrication of plasmonic nanostructures without significant distortion of the plasmonic characteristics. As determined from the homogeneous linewidth of the resonance scattering spectrum of individual gold nanorods, an ultrathin Ti layer reduces the plasmon dephasing time significantly, and it reduces the plasmon scattering amplitude drastically. The increased damping rate and decreased plasmon amplitude are due to the dissipative dielectric function of Ti and the chemical interface plasmon damping where the conduction electrons are transferred across the metal-metal interface. In addition, a pronounced red shift due to the Ti adhesion layer, more than predicted using electromagnetic simulation, suggests the prevalence of interfacial reactions. By extending the experiment to conductively coupled ring-rod nanostructures, it is shown that a sharp Fano-like resonance feature is smeared out due to the Ti layer. Alternatively, vapor deposition of (3-mercaptopropyl)trimethoxysilane on gently cleaned and activated lithographic patterns functionalizes the glass surface sufficiently to link the gold nanostructures to the surface by sulfur-gold chemical bonds without observable plasmon damping effects.

Theta-shaped plasmonic nanostructures: bringing "dark" multipole plasmon resonances into action via conductive coupling.

Quadrupole plasmon and (octupolar) Fano resonances are induced in lithographically fabricated theta-shaped ring-rod gold nanostructures. The optical response is characterized by measuring the light scattered by individual nanostructures. When the nanorod is brought within 3 nm of the ring wall, a weak quadrupolar resonance is observed due to capacitive coupling, and when a necklike conductive bridge links the nanorod to the nanoring the optical response changes dramatically bringing the quadrupolar resonance into prominence and creating an octupolar Fano resonance. The Fano resonance is observed due to the destructive interference of the octupolar resonance with the overlapping and broadened dipolar resonance. The quadrupolar and Fano resonances are further enhanced by capacitive coupling (near-field interaction) that is favored by the theta-shaped arrangement. The interpretation of the data is supported by FDTD simulation.

Effects of isomer coexistence and solvent-induced core switching in the photodissociation of bare and solvated (CS2)2(-) anions.

The photodissociation of the (CS(2))(2)(-) dimer anion, known to exist in the form of several electronic and structural isomers, has been investigated at 532, 355, and 266 nm. The observed anionic fragments are CS(2)(-) and C(2)S(2)(-) at 532 nm, and C(2)S(2)(-), CS(2)(-), CS(3)(-), S(2)(-), and S(-) at 355 and 266 nm. In addition to the photon energy, the fractional yields of the photofragments depend on the ion source conditions and solvation of the dimer anion. Specifically, the (C(2)S(2)(-) + S(2)(-))/CS(2)(-) product ratio is significantly higher when (CS(2))(2)(-) is formed in the presence of water in the precursor gas mixture, even though the parent anion itself does not include H(2)O. On the other hand, an abrupt decrease in the above product ratio is observed upon the addition of solvent molecules (CS(2) or H(2)O) to the (CS(2))(2)(-) anion. Since the variation of this product ratio exhibits positive correlation with the relative intensity of the photoelectron band assigned to the C(2v) ((2)B(1)) covalent structure of C(2)S(4)(-) by Habteyes et al. [J. Phys. Chem. A 112, 10134 (2008)], this structure is suggested as the primary origin of the C(2)S(2)(-) and S(2)(-) photoproducts. The switching of the fragmentation yield from C(2)S(2)(-) and S(2)(-) to other products upon solvation is ascribed to the diminished presence of the C(2v) ((2)B(1)) dimer-anion structure relative to the CS(2)(-) based clusters. This population shift is attributed to the more effective solvation of the latter. The CS(2)(-) based clusters are suggested as the origin of the S(-) photoproduct, while CS(3)(-) is formed through the secondary S(-) + CS(2) intracluster association reaction.

Observation and characterization of the CH3S(O)CH- and CH3S(O)CH- x H2O carbene anions by photoelectron imaging and photofragment spectroscopy.

We report the observation of the CH(3)S(O)CH(-) and CH(3)S(O)CH(-) x H(2)O carbene anions formed upon overall H(2)(+) abstraction from dimethyl sulfoxide by O(-). Photoelectron spectroscopy reveals singlet and triplet carbenes for the remaining neutral, with the singlet state assigned as the ground state. Although some formation of the distonic CH(2)S(O)CH(2)(-) radical anion is also expected, no conclusive evidence of the presence of this isomer is found. The photoelectron spectrum of HCSO(-) is also reported for the first time. Photofragmentation of CH(3)S(O)CH(-) with 532 nm light reveals two main types of anionic products: a dominant HCSO(-) fragment, resulting from methyl elimination, and a less intense SO(-) product. For the monohydrated anion, an additional SO(-) x H(2)O fragment is observed. Intriguingly, both the SO(-) x H(2)O and SO(-) products are produced with much higher yields in the fragmentation of CH(3)S(O)CH(-) x H(2)O, compared to the SO(-) yield from the dissociation of the bare CH(3)S(O)CH(-) anion. Two possible pathways are proposed as likely mechanisms for the SO(-)-based photoproducts, both involving a photoinduced intramolecular rearrangement and the formation of a C-C bond.

Relaxation of (CS2)2(-) to its global minimum mediated by water molecules: photoelectron imaging study.

The coexistence of several isomers of (CS 2) 2 (-) is examined via photoelectron imaging at 355 and 266 nm. Assisted by theoretical calculations, the bands in the photoelectron spectra are assigned to the CS 2 (-).CS 2 ion-molecule complex ( C s symmetry, (2)A' electronic state) and two covalently bound dimer-anion structures: C 2 v ( (2)B 1) and D 2 h ( (2)B 3g). The isomer distribution depends sensitively on the ion source conditions, particularly the presence of water in the precursor gas mixture. The intensity variation of the photoelectron bands suggests that the presence of water enhances the formation of the global-minimum C 2 v ( (2)B 1) structure, particularly relative to the metastable (local-minimum) ion-molecule complex. This trend is rationalized with two assumptions. The first is that the presence of H 2O at the cluster formation stage facilitates the nonadiabatic transitions necessary for reaching the global-minimum dimer-anion equilibrium when starting from the CS 2 (-) + CS 2 asymptote. The second is that the initial clusters formed in the presence of water tend to have, on average, more internal energy, which is needed for overcoming the potential energy barriers separating the metastable equilibria from the global-minimum structure. As the covalent bonds are formed, excess solvent molecules are evaporated from the cluster, giving rise to stable (CS 2) 2 (-) dimer anions. In the (CS 2) n (-), n >or= 3, and (CS 2) 2 (-)(H 2O) m , m > 0, clusters, the population of the covalent-dimer core structures diminishes drastically due to more favorable solvent interactions with the monomer-anion (i.e., CS 2 (-)) core.

Electron binding motifs in the (CS2)n- (n>4) cluster anions.

Photoelectron imaging spectroscopy of (CS(2))(n) (-), n>4, reveals a new state with an electron binding energy smaller than that of any of the corresponding CS(2) (-) and C(2)S(4) (-) states known to date. With support from ab initio calculations, two long-lived, metastable binding motifs with small electron binding energies are discussed for these clusters. The first is a solvent network permeating state, where the excess electron is delocalized over a number of linear CS(2) molecules. The second is an excited (2)B(1) state of the core CS(2) (-) anion stabilized at a slightly bent geometry by the solvation interactions. Based on the observed solvation-induced shifts in binding energy, the second motif is favored.

Solvent resonance effect on the anisotropy of NO(-)(N(2)O)(n) cluster anion photodetachment.

Photodetachment from NO(-)(N(2)O)(n) cluster anions (n< or =7) is investigated using photoelectron imaging at 786, 532, and 355 nm. Compared to unsolvated NO(-), the photoelectron anisotropy with respect to the laser polarization direction diminishes drastically in the presence of the N(2)O solvent, especially in the 355 nm data. In contrast, a less significant anisotropy loss is observed for NO(-)(H(2)O)(n). The effect is attributed to photoelectron scattering on the solvent, which in the N(2)O case is mediated by the (2)Pi anionic resonance. No anionic resonances exist for H(2)O in the applicable photoelectron energy range, in line with the observed difference between the photoelectron images obtained with the two solvents. The momentum-transfer cross section, rather than the total scattering cross section, is argued to be an appropriate physical parameter predicting the solvent effects on the photoelectron angular distributions in these cluster anions.

Photodissociation of CO2 - in water clusters via Renner-Teller and conical interactions.

The photochemistry of mass selected CO(2) (-)(H2O)(m), m=2-40 cluster anions is investigated using 266 nm photofragment spectroscopy and theoretical calculations. Similar to the previous 355 nm experiment [Habteyes et al., Chem. Phys. Lett. 424, 268 (2006)], the fragmentation at 266 nm yields two types of anionic products: O(-)(H2O)(m-k) (core-dissociation products) and CO(2) (-)(H2O)(m-k) (solvent-evaporation products). Despite the same product types, different electronic transitions and dissociation mechanisms are implicated at 355 and 266 nm. The 355 nm dissociation is initiated by excitation to the first excited electronic state of the CO(2) (-) cluster core, the 1 (2)B(1)(2A") state, and proceeds via a glancing Renner-Teller intersection with the ground electronic state at a linear geometry. The 266 nm dissociation involves the second excited electronic state of CO(2) (-), the 2 (2)A(1)(2A') state, which exhibits a conical intersection with the 3 (2)B(2)(A') state at a bent geometry. The asymptotic O(-) based products are believed to be formed via this 3 (2)B(2)(A') state. By analyzing the fragmentation results, the bond dissociation energy of CO(2) (-) to O(-)+CO in hydrated clusters (m> or =20) is estimated as 2.49 eV, compared to 3.46 eV for bare CO(2) (-). The enthalpy of evaporation of one water molecule from asymptotically large CO(2) (-)(H(2)O)(m) clusters is determined to be 0.466+/-0.001 eV (45.0+/-0.1 kJ/mol). This result compares very favorably with the heat of evaporation of bulk water, 0.456 eV (43.98 kJ/mol).

Photodetachment and photofragmentation pathways in the [(CO2)2(H2O)m]- cluster anions.

The mass-selected [(CO(2))(2)(H(2)O)(m)](-) cluster anions are studied using a combination of photoelectron imaging and photofragment mass spectroscopy at 355 nm. Photoelectron imaging studies are carried out on the mass-selected parent cluster anions in the m=2-6 size range; photofragmentation results are presented for m=3-11. While the photoelectron images suggest possible coexistence of the CO(2) (-)(H(2)O)(m)CO(2) and (O(2)CCO(2))(-)(H(2)O)(m) parent cluster structures, particularly for m=2 and 3, only the CO(2) (-) based clusters are both required and sufficient to explain all fragmentation pathways for m>/=3. Three types of anionic photofragments are observed: CO(2) (-)(H(2)O)(k), O(-)(H(2)O)(k), and CO(3) (-)(H(2)O)(k), k6) is attributed to hindrance from the H(2)O molecules.