Optical Spectra Properties of Neutral Zn-Doped Au<Subscript>20</Subscript> Nanoclusters by First-Principles Calculations

Gold nanoclusters are promising for the potential applications in photothermal therapy, but visible optical absorption of Au₂₀ (gap = 1.818 eV) limits the in vivo applications. A first-principles study has been performed to evaluate the electronic and optical properties of neutral Au_20-n Zn _n (n = 0–4) clusters. We have employed the Perdew–Burke–Ernzerhof form of generalized gradient approximation in the frame work of density functional theory. The results of imaginary part of the dielectric function e₂ (w) \varepsilon_{2} (\omega ) and optical absorption indicate that the optical transition of Au_20-n Zn _n between HOMO and LUMO has shifted to the near-infrared range as the Zn atoms incorporation. The subsequent transition energy level shows the Zn s and p states have obvious contributions to both of the HOMO and LUMO. The Zn-doped Au₂₀ clusters show the tunable optical properties, and have potential application for in vivo photothermal therapy.     

Noble metal nanocrystals: plasmon electron transfer photochemistry and single-molecule Raman spectroscopy

The excited electronic states of noble metal Au and Ag nanocrystals are very different than those of molecules. Ag and Au nanocrystal optical transitions (plasmons) in the visible can be so intense that they significantly modify the local electromagnetic field. Also, coherent elastic Rayleigh light scattering is stronger than normal electronic absorption of photons for larger nanocrystals. These two facts make Au and Ag nanocrystals ideal nanoantennas, in that they focus incident light into the local neighborhood of subwavelength size. Surface-enhanced Raman scattering (SERS), in which the Raman scattering rate of nearby molecules increases by many orders of magnitude, is a consequence of this nanoantenna effect. Metallic nanocrystals also have no band gap; this makes them extraordinarily polarizable. Their electronic transitions sense the local environment. An extreme case is the interaction of two 30 nm Ag nanocrystals separated by a 1 nm gap. Their mutual polarization completely transforms the nature of the metallic excited electronic state. Single particles have an excited state uniformly distributed throughout the interior, while the nanocrystal dimer has its excited state localized on the metal surface in the junction. This creates an electromagnetic "hot spot" in the junction, enabling the observation of single-molecule SERS. The fact that surface molecules are typically chemisorbed and exchange electrons with the metal has interesting chemical consequences. First, the enhanced Raman intensities are controlled by quantum mechanical coupling of the molecular lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) with the optically excited electrons in the metal. Second, charge-transfer photochemistry can result from metal plasmon excitation. In crystalline Ag nanocrystals the photochemistry quantum yield can be high because the nanocrystal surface dominates plasmon nonradiative relaxation. Colloidal Ag nanocrystals stabilized by sodium citrate build up a photovoltage under visible excitation, caused by irreversible "hot hole" photo-oxidation of adsorbed citrate anion. This creates a driving force for photochemical transformation of round 8 nm Ag seeds into 70 nm single-crystal disk prisms under room lights, in a novel type of light-driven Ostwald ripening.     

Quantum chemical studies on corrosion inhibition for series of thio compounds on mild steel in hydrochloric acid

Quantum chemical calculations were performed on ten thio compounds using semi-empirical method PM3 within program package of Material Studio 5.5. The effect of molecular structure on the corrosion inhibition efficiency was investigated using the quantum chemical calculations. The electronic properties such as highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) energy levels, (LUMO–HOMO) energy gap, dipole moment (λ) and fraction of electron transfer (ΔN) were calculated and discussed. A relationship between the corrosion inhibition efficiency and several quantum parameters was established with coefficient correlation (R²) of 0.8894.     

Gold supported on thin oxide films: from single atoms to nanoparticles

[Figure: see text]. Historically, people have prized gold for its beauty and the durability that resulted from its chemical inertness. However, even the ancient Romans had noted that finely dispersed gold can give rise to particular optical phenomena. A decade ago, researchers found that highly dispersed gold supported on oxides exhibits high chemical activity in a number of reactions. These chemical and optical properties have recently prompted considerable interest in applications of nanodispersed gold. Despite their broad use, a microscopic understanding of these gold-metal oxide systems lags behind their application. Numerous studies are currently underway to understand why supported nanometer-sized gold particles show catalytic activity and to explore possible applications of their optical properties in photonics and biology. This Account focuses on a microscopic understanding of the gold-substrate interaction and its impact on the properties of the adsorbed gold. Our strategy uses model systems in which gold atoms and clusters are supported on well-ordered thin oxide films grown on metal single crystals. As a result, we can investigate the systems with the rigor of modern surface science techniques while incorporating some of the complexity found in technological applications. We use a variety of different experimental methods, namely, scanning probe techniques (scanning tunneling microscopy and spectroscopy, STM and STS), as well as infrared (IR), temperature-programmed desorption (TPD), and electron paramagnetic resonance (EPR) spectroscopy, to evaluate these interactions and combine these results with theoretical calculations. We examined the properties of supported gold with increasing complexity starting from single gold atoms to one- and two-dimensional clusters and three-dimensional particles. These investigations show that the binding of gold on oxide surfaces depends on the properties of the oxide, which leads to different electronic properties of the Au deposits. Changes in the electronic structure, namely, the charge state of Au atoms and clusters, can be induced by surface defects such as color centers. Interestingly, the film thickness can also serve as a parameter to alter the properties of Au. Thin MgO films (two to three monolayer thickness) stabilize negatively charged Au atoms and two-dimensional Au particles. In three dimensions, the properties of Au particles bigger than 2-3 nm in diameter are largely independent of the support. Smaller three-dimensional particles, however, showed differences based on the supporting oxide. Presumably, the oxide support stabilizes particular atomic configurations, charge states, or electronic properties of the ultrasmall Au aggregates, which are in turn responsible for this distinct chemical behavior.     

Modeling heterogeneous catalysts: metal clusters on planar oxide supports

Model catalysts consisting of Au and Ag clusters of varying size have been prepared on single crystal TiO₂(110) and ultra-thin films of TiO₂, SiO₂ and Al₂O₃. The morphology, electronic structure, and catalytic properties of these Au and Ag clusters have been investigated using low-energy ion scattering spectroscopy (LEIS), temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM) and spectroscopy (STS) with emphasis on the unique properties of clusters <5.0 nm in size. Motivating this work is the recent literature report that gold supported on TiO₂ is active for various reactions including low-temperature CO oxidation and the selective oxidation of propylene. These studies illustrate the novel and unique physical and chemical properties of nanosized supported metal clusters.     

Electronically coupled porphyrin-arene dyads for dye-sensitized solar cells

An acetylene-linked porphyrin-perylene anhydride and an acetylene-linked porphyrin-naphthalic anhydride have been synthesized; the highly conjugated acetylenic bridge in these porpyrins efficiently mediates electronic interaction between the porphyrin and perylene units to extend the π-conjugation of the porphyrin dye and to cause both broadening and red shifts of both the Soret and Q absorption bands. This condition is a useful feature for efficient dye-sensitized solar cell applications. The optical, electrochemical and photovoltaic properties of the new linked anhydrides show that the HOMO–LUMO gap decreased upon extension of π-conjugation, indicating a strong electronic coupling between the porphyrin and the perylene or naphthalene unit.     

Photoelectrochemical analysis of size-dependent electronic structures of gold clusters supported on TiO2

Size-dependent electronic structures around the Fermi level of glutathione-protected gold clusters (0.9-1.4 nm in core diameter) were analyzed on the basis of photoinduced charge separation at the interface between the gold cluster and TiO(2). Electron levels such as HOMO and LUMO were estimated from the dependencies of the photocurrents on the irradiation wavelength and the standard electrode potentials of electron donors employed. The potential of the occupied levels involved in the charge separation under visible or near infrared light shifts negatively as the cluster size increases.     

Optical properties of Ag nanoparticle-polymer composite film based on two-dimensional Au nanoparticle array film

The nanocomposite polyvinyl pyrrolidone (PVP) films containing Ag nanoparticles and Rhodamine 6G are prepared on the two-dimensional distinctive continuous ultrathin gold nanofilms. We investigate the optical properties and the fluorescence properties of silver nanoparticles-PVP polymer composite films influenced by Ag nanoparticles and Au nanoparticles. Absorption spectral analysis suggests that the prominently light absorption in Ag nanowire/PVP and Ag nanowire/PVP/Au film arises from the localized surface plasmon resonance of Ag nanowire and Au nanofilm. The enhanced fluorescence is observed in the presence of Ag nanowire and Au nanofilm, which is attributed to the excitation of surface plasmon polariton resonance of Ag nanowire and Au nanofilm. The gold nanofilm is proven to be very effective fluorescence resonance energy transfer donors. The fabricated novel structure, gold ultrathin continuous nanofilm, possesses high surface plasmon resonance properties and prominent fluorescence enhancement effect. Therefore, the ultrathin continuous gold nanofilm is an active substrate on nanoparticle-enhanced fluorescence.     

Conjugated polymer mediated synthesis of nanoparticle clusters and core/shell nanoparticles

Two water soluble conjugated polymers, poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) and ammonium ion stabilized poly(phenylene vinylene) (P2), are found to be able to reduce noble metal ions to zero-valent metals via a direct chemical deposition technique. Au nanoparticle clusters can be obtained through reduction of Au³⁺ ions by PEDOT:PSS and the electronic coupling between them can be controlled by HAuCl₄ concentration. Core/shell Ag/polymer nanostructures are prepared from reduction of Ag⁺ ions by P2, which have a ppb detection limit for 4-MBA using surface-enhanced Raman spectroscopy (SERS). This conjugated polymer mediated synthesis of metal nanoparticles may open a new avenue for fabricating nanomaterials and nanocomposites with tunable optical properties that are dominated by their structure and electronic coupling between nanoparticles.     

Probing the electronic properties and structural evolution of anionic gold clusters in the gas phase

Gold nanoparticles have been discovered to exhibit remarkable catalytic properties in contrast to the chemical inertness of bulk gold. A prerequisite to elucidate the molecular mechanisms of the catalytic effect of nanogold is a detailed understanding of the structural and electronic properties of gold clusters as a function of size. In this review, we describe joint experimental studies (mainly photoelectron spectroscopy) and theoretical calculations to probe the structural properties of anionic gold clusters. Electronic properties and structural evolutions of all known Au(n)(-) clusters as experimentally confirmed to date are summarized, covering the size ranges of n = 3-35 and 55-64. Recent experimental efforts in resolving the isomeric issues of small gold clusters using Ar-tagging, O(2)-titration and isoelectronic substitution are also discussed.     

The halogen analogs of thiolated gold nanoclusters

Is it possible to replace all the thiolates in a thiolated gold nanocluster with halogens while still maintaining the geometry and the electronic structure? In this work, we show from density functional theory that such halogen analogs of thiolated gold nanoclusters are highly likely. Using Au(25)X(18)(-) as an example, where X = F, Cl, Br, or I replaces -SR, we find that Au(25)Cl(18)(-) demonstrates a high similarity to Au(25)(SR)(18)(-) by showing Au-Cl distances, Cl-Au-Cl angles, band gap, and frontier orbitals similar to those in Au(25)(SR)(18)(-). DFT-based global minimization also indicates the energetic preference of staple formation for the Au(25)Cl(18)(-) cluster. The similarity between Au(m)(SR)(n) and Au(m)X(n) could be exploited to make viable Au(m)X(n) clusters and to predict structures for Au(m)(SR)(n).     

Mechanical and electronic properties of ultrathin nanodiamonds under uniaxial compressions

Mechanical and electronic properties of ultrathin hydrogenated nanodiamonds (with diameters from 0.71 nm to 1.4 nm) under uniaxial compression have been investigated by means of density functional theory calculations. The computed Young's moduli of nanodiamonds are lower than the bulk value and increase with size, which can be fitted to an empirical function of diameter. Similar to the bulk diamond, the HOMO–LUMO gaps of nanodiamond reduces under uniaxial strain, implying tunable electronic properties via mechanical deformations.     

Poly(dimethylsiloxane)‐containing thermoplastic elastomer/gold–silver alloy nanocomposites for thermally/oxidatively stable and antimicrobial coating

Polymer materials with embedded silver (Ag) nanoparticle (NP) are of considerable interest owing to their enhanced antimicrobial activity and physical properties compared to host polymer. Antimicrobial and thermally/oxidatively stable coating not only enhances the durability of the coated material but also reduces the growth of bacteria/fungus and thus reduces the chance of infection. For this purpose, we have prepared polydimethylsiloxane‐containing predominantly poly(meth)acrylates‐based pentablock thermoplastic elastomer (TPE)/gold (Au)–Ag alloy nanocomposites (NCs) with antimicrobial activity and enhanced physical properties. In situ simultaneous reduction of appropriate amount of metal salts in the presence of block copolymer produced Au–Ag NPs of size 5–10 nm. Such embedded 5–10 nm sized particles (loading, 0.1–0.2 wt%) improved the mechanical property, thermal/oxidative stability, and antimicrobial activity of the NCs. The NC films also exhibited tunable surface wetting behavior and optical properties. The NC films showed low level of Ag leaching as confirmed by inductively coupled plasma spectrometer and UV–visible spectroscopy. Improved thermal/oxidative resistance of the TPE/Au–Ag alloy NCs enhanced antimicrobial activity, together with low level of leaching characteristic of the embedded NPs deemed suitable for further use of these NCs material for antimicrobial and oxidatively stable coating applications. POLYM. COMPOS., 36:2103–2112, 2015. © 2014 Society of Plastics Engineer     

Quantum sized gold nanoclusters with atomic precision

Gold nanoparticles typically have a metallic core, and the electronic conduction band consists of quasicontinuous energy levels (i.e. spacing δ ? k(B)T, where k(B)T is the thermal energy at temperature T (typically room temperature) and k(B) is the Boltzmann constant). Electrons in the conduction band roam throughout the metal core, and light can collectively excite these electrons to give rise to plasmonic responses. This plasmon resonance accounts for the beautiful ruby-red color of colloidal gold first observed by Faraday back in 1857. On the other hand, when gold nanoparticles become extremely small (<2 nm in diameter), significant quantization occurs to the conduction band. These quantum-sized nanoparticles constitute a new class of nanomaterial and have received much attention in recent years. To differentiate quantum-sized nanoparticles from conventional plasmonic gold nanoparticles, researchers often refer to the ultrasmall nanoparticles as nanoclusters. In this Account, we chose several typical sizes of gold nanoclusters, including Au(25)(SR)(18), Au(38)(SR)(24), Au(102)(SR)(44), and Au(144)(SR)(60), to illustrate the novel properties of metal nanoclusters imparted by quantum size effects. In the nanocluster size regime, many of the physical and chemical properties of gold nanoparticles are fundamentally altered. Gold nanoclusters have discrete electronic energy levels as opposed to the continuous band in plasmonic nanoparticles. Quantum-sized nanoparticles also show multiple optical absorption peaks in the optical spectrum versus a single surface plasmon resonance (SPR) peak at 520 nm for spherical gold nanocrystals. Although larger nanocrystals show an fcc structure, nanoclusters often have non-fcc atomic packing structures. Nanoclusters also have unique fluorescent, chiral, and magnetic properties. Due to the strong quantum confinement effect, adding or removing one gold atom significantly changes the structure and the electronic and optical properties of the nanocluster. Therefore, precise atomic control of nanoclusters is critically important: the nanometer precision typical of conventional nanoparticles is not sufficient. Atomically precise nanoclusters are represented by molecular formulas (e.g. Au(n)(SR)(m) for thiolate-protected ones, where n and m denote the respective number of gold atoms and ligands). Recently, major advances in the synthesis and structural characterization of molecular purity gold nanoclusters have made in-depth investigations of the size evolution of metal nanoclusters possible. Metal nanoclusters lie in the intermediate regime between localized atomic states and delocalized band structure in terms of electronic properties. We anticipate that future research on quantum-sized nanoclusters will stimulate broad scientific and technological interests in this special type of metal nanomaterial.     

Vibrational and electronic properties of PPV-derived co-polymers: PPV-ether and C1-4PPV-ether

In this paper a combined experimental and quantum chemical study of two co-polymers, derived from poly(phenylene vinylene), referred to as PPV-ether and C_1-4PPV-ether, is presented. First, the geometries of these co-polymers were fully optimized. In fact, semiempirical, ab initio and density functional theory (DFT) have been used to investigate the ground-state properties of these co-polymers. Then, the electronic properties, lying in the excitation between the highest occupied molecular orbitals (HOMO) and the lowest unoccupied molecular orbitals (LUMO), the transition eigenvalues, the density of states together with other relevant physical quantities, were investigated. Moreover, the vibrational properties and the force constants are determined. In fact, the calculated results have well reproduced the available experimental data in which the pattern of dialkoxy-substitution is found to have a large effect.     

An interpretation on the origin of the specular reflectance change caused by the submonolayer formation of foreign metals on some precious metal electrodes

The optical properties of foreign metal submonolayers formed on Au, Ag, Cu, Pt and Pd electrodes through the underpotential deposition have been investigated by specular reflectivity measurement. Based on the spectral characteristics, 14 adsorbate-substrate systems were classified into 2 groups. The first group, involving Bi on Au, Cu on Au, Pb on Au, Tl on Au, Tl on Ag and Cd on Cu, is characterized by the similarity of the optical properties of the adsorbed metal in the submonolayer to those of bulk metal. The first monolayer was found to form through several submonolayer stages, in which the optical constants are slightly different from each other. In the second group, involving Cd on Au, In on Au, Sn on Au, Ag on Pt, Bi on Pt, Cu on Pt, Pb on Pt and Bi on Pd, the spectra of submonolayer observed experimentally differ from those calculated with the assumption that the optical properties of adatom and substrate are the same as those of corresponding bulk metal. The difference in the work functions between adsorbate and substrate materials in this group is larger than those in the first group.From these findings, some considerations were made to interpret the origin of the specular reflectance change due to the presence of metal adlayer on the electrode surface. The results allow a tentative conclusion that the reflectivity change is predominantly attributed to the optical properties of the adsorbed submonolayer, but at the same time the work function of the substrate and the interband transition in visible should also be taken into consideration.     

Electronic structure and properties of alternating donor-acceptor conjugated copolymers: 3,4-Ethylenedioxythiophene (EDOT) copolymers and model compounds

The electronic structure and properties of 3,4-ethylenedioxythiophene (EDOT) based alternating donor-acceptor conjugated copolymers and their model compounds were studied by the density functional theory (DFT) at the B3LYP level with 6-31G or 6-31G** basis set. The acceptors investigated include thiazole (Z), thiadiazole (D), thienopyrazine (TP), thienothiadiazole (TD), thiadiazolothienopyrazine (TPD), quinoxaline (BP), benzothiadiazole (BD), pyrazinoquinoxaline (BPP), benzobisthiadiazole (BDD), and thiadiazoloquinoxaline (BDP). The torsional angle, intramolecular charge transfer, bridge bond length, and bond length alternation were analyzed and correlated with the electronic properties. It was found that the geometries of the donor-acceptor materials were significantly affected by the ring size and intramolecular charge transfer. The HOMO level, LUMO level, and band gap of the model compounds were well correlated with the acceptor strength. However, the electronic properties of the copolymers did not vary systematically with the acceptor strength due to the change in geometry from model compound to polymer. The aromatic geometry of EDOT-TP model compound is transformed to quinoid in the corresponding copolymer and results in a small band gap (E_g) of 0.97 eV. Large intramolecular charge transfer and the small bond length alternation in the EDOT-BDP copolymer resulted in an E_g of 0.7 eV. Hence, these two polymers could have potential applications for transparent conductors or photovoltaic devices. The small effective masses and large HOMO and LUMO bandwidths of PEDOT-TP and PEDOT-BDP make them potential materials for ambipolar thin film transistors. The theoretical results suggest that both the acceptor strength and the stable geometry contribute significantly to the electronic properties of alternating donor-acceptor conjugated copolymers.     

A theoretical investigation on the properties of the new poly(N‐vinylcarbazole)‐3‐methylthiophene (PVK‐3MeT) synthesized graft copolymer

In this article, we present quantum chemical calculations, based on density functional theory (DFT), performed to investigate the geometries and the opto‐electronic properties of a new synthesized graft copolymer based on poly(N‐vinylcarbazole) (PVK) and poly(3‐methylthiophene) (PMeT) named PVK‐3MeT. First, we have theoretically computed and compared the structural, optical, and vibrational parameters of both neutral and doped states. In addition, the excited state was theoretically obtained by the ab initio RCIS/STO‐3G method. To assign the absorption and emission peaks observed experimentally, we computed the energies of the lowest singlet excited state with the time‐dependent density functional theory (TD‐DFT) method. Electronic parameters such as the HOMO‐LUMO band gap, the ionization potential (IP), and electron affinity (EA) are extracted. Calculations show that the PVK‐3MeT copolymer is nonplanar in its ground neutral state. Meanwhile, upon doping or photoexcitation, an enhancement of the planarity is observed, resulting on a decrease of the inter‐ring torsion angle between 3‐methylthiophene units. Such modifications in the geometric parameters induce a dramatic change on the HOMO and LUMO orbitals in the doped or excited states. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Theoretical study of charge transfer mechanism in fullerene-phenyl-phenothiazine compound: A real-space analysis

Quantum chemistry methods as well as two-dimensional (2D) and three-dimensional (3D) real-space analysis have been conducted to study the photo-induced intramolecular charge-transfer (ICT) and excited state properties of fullerene-phenylphenothiazine, which has recently been developed for solar cells. Firstly, we obtained the energy levels and spatial distributions of HOMO/LUMO, energy gap (ΔEH-L) and excitation energies on the basis of quantum chemistry study. Secondly, two-dimensional (2D) and three-dimensional (3D) real-space analysis were used to visualize the CT process and to reveal the nature of the excited states. In the above analyses, the 2D real-space analysis of the transition density matrix provided information about the electron-hole coherence, and the 3D real-space analysis of charge difference density enabled the visualization of the orientation and result of the ICT. The results of real-space analysis directly indicate that some states are ICT states, and others belong to locally excited states. Moreover, according to the generalized Mulliken Hush theory, we calculated the electronic coupling matrix elements and predict that electron transfer for some ICT states more easily takes place than that for some locally excited states.     

Band structure and absorption spectrum of double-walled zigzag carbon nanotubes in an electric field

The electronic structure of the (9, 0)-(18, 0) double-walled zigzag carbon nanotubes in the presence of a uniform transverse electric field is studied by the tight-binding model. The electric field could induce the semiconductor-metal transition, change the direct gap into the indirect gap, alter the subband curvatures, destroy the double degeneracy, produce the new band-edge states, make more subbands group around the Fermi level, and widen the π-band width. Such effects are directly reflected in density of states and optical excitation spectra. The absorption spectra exhibit a lot of prominent peaks, mainly owing to the rich one-dimensional energy subbands. The intensity, the number, and the frequency of absorption peaks are strongly modulated by the electric field. The modulation of electronic and optical properties is amplified by the parallel magnetic field. The predicted electronic and optical properties can be, respectively, verified by the conductance measurements and the optical spectroscopy.