Ab initio molecular dynamics simulation of a medium-sized water cluster anion: from an interior to a surface-located excess electron via a delocalized state

We present a computational study of the structure and dynamics of an excess electron in a medium-sized water cluster aimed at addressing the question of interior vs exterior solvation. Ab initio Born-Oppenheimer molecular dynamics simulations were performed within the DFT framework, employing a hybrid Gaussian and plane-wave formalism together with the PBE exchange-correlation functional and norm-conserving pseudopotentials. Analysis of a 15-ps trajectory allowed us to reach the following conclusions: (i) the excess electron is predominantly located at the cluster surface (even if it is initially placed in the interior), (ii) the computed electron binding energies correlate with the electron localization rather than with its bulk vs surface location, and (iii) a dynamical interconversion between two different H-bond patterns around the electron occurs. The computed electron binding energies and the most relevant features of the IR spectrum are in a very good agreement with results of previous experimental studies.     

Non-nuclear attractor of electron density as a manifestation of the solvated electron

Two or more polar molecules can trap an excess electron either in a dipole-bound fashion where it is located outside of the cluster (dipole-bound electron) or inside the cluster (solvated electron). The topology of the electron density in dipole-bound and solvated-electron clusters has been examined for the paradigm (HF)3- cluster. As spatial confinement of the excess electron increases, a non-nuclear maximum (or attractor) of the electron density eventually forms, which suggests that the solvated electron can be described as a topological atom with its own set of physicochemical properties.     

Immobilization of a Bacterial Cytochrome P450 Monooxygenase System on a Solid Support

Bacterial cytochrome P450s (P450s), which catalyze regio‐ and stereoselective oxidations of hydrocarbons with high turnover rates, are attractive biocatalysts for fine chemical production. Enzyme immobilization is needed for cost‐effective industrial manufacturing. However, immobilization of P450s is difficult because electron‐transfer proteins are involved in catalysis and anchoring these can prevent them from functioning as shuttle molecules for carrying electrons. We studied a heterotrimeric protein‐mediated co‐immobilization of a bacterial P450, and its electron‐transfer protein and reductase. Fusion with subunits of a heterotrimeric Sulfolobus solfataricus proliferating cell nuclear antigen (PCNA) enabled immobilization of the three proteins on a solid support. The co‐immobilized enzymes catalyzed monooxygenation because the electron‐transfer protein fused to PCNA via a single peptide linker retained its electron‐transport function.     

Polydopamine as a Biomimetic Electron Gate for Artificial Photosynthesis

We report on the capability of polydopamine (PDA), a mimic of mussel adhesion proteins, as an electron gate as well as a versatile adhesive for mimicking natural photosynthesis. This work demonstrates that PDA accelerates the rate of photoinduced electron transfer from light‐harvesting molecules through two‐electron and two‐proton redox‐coupling mechanism. The introduction of PDA as a charge separator significantly increased the efficiency of photochemical water oxidation. Furthermore, simple incorporation of PDA ad‐layer on the surface of conducting materials, such as carbon nanotubes, facilitated fast charge separation and oxygen evolution through the synergistic effect of PDA‐mediated proton‐coupled electron transfer and the high conductivity of the substrate. Our work shows that PDA is an excellent electron acceptor as well as a versatile adhesive; thus, PDA constitutes a new electron gate for harvesting photoinduced electrons and designing artificial photosynthetic systems.     

TiO2纳米晶复合纳米棒染料敏化太阳能电池

通过二次水热法合成锐钛矿TiO₂纳米棒(ANR). 采用X射线衍射(XRD)、场发射扫描电镜(FE-SEM)和透射电镜(TEM)等手段对其进行表征. 通过调节ANR和锐钛矿纳米颗粒(ANP)的掺杂比例来增加TiO₂纳米晶膜的光捕获效率和电子传输速率, 并对比了单层结构(ANR+ANP)和双层结构(ANP/(ANR+ANP))的纳米晶膜光阳极的光电转化性能. 在AM 1.5、光强100 mW·cm^-2的模拟太阳光下测试, 染料N719敏化的双层结构太阳能电池光电转化效率达7.3%, 比相同条件下单层纯ANP光阳极器件的光电转化效率(6.1%)提高了20%.     

Constriction of a microwave-induced plasma by a magnetic pinch

The microwave-induced plasma has been widely studied as a spectrochemical excitation source. The plasma is generally maintained in a quartz tube, and energy coupled via a cavity or antenna. Previous work has shown the importance of the electron density; plasma performance is improved as the instrumental parameters are adjusted to increase the electron density. Another method to increase the electron density is to constrict the plasma. Additionally, energy losses via wall-collision would be decreased if the plasma were moved away from the walls. This communication presents such a study, in which the plasma is ‘pinched’ by the application of an external magnetic field. Preliminary results show an increase in intensity by a factor of two. The constriction also tends to improve the atomization processes. Measurements performed on plasmas which contain carbon monoxide show a greater increase in the carbon atomic emission than the carbon monoxide molecular emission.     

Role of vibrationally excited NO in promoting electron emission when colliding with a metal surface: a nonadiabatic dynamic model

A nonadiabatic quantum dynamic model has been developed to study the process of electron emission from a low-work-function metal surface. The process is initiated by scattering a highly vibrationally excited NO molecule from a surface composed of a Cs layer covering a Ru crystal. The model addresses the increasing quantum yield of the electron emission as a function of the molecular vibrational excitation and incident kinetic energy. The reaction mechanism is identified as a long-range harpooning electron transfer to a molecular ion which is then accelerated toward the surface. Upon impact, the molecular ion emits its excess electron.     

Single electron densities: a new tool to analyze molecular wavefunctions

A new partitioning scheme for the electron density of a many-electron wavefunction into single electron densities is proposed. These densities are based on the most probable arrangement of the electrons in an atom or molecule. Therefore, they contain information about the electron-electron interaction and, most notably, the Fermi hole due to the antisymmetry of the many-electron wavefunction. The single electron densities overlap and can be combined to electron pair distributions close to the qualitative electron pairs that represent, for instance, the basis of the valence shell electron pair repulsion model. Single electron analyses are presented for the water, ethane, and ethene molecules. The effect of electron correlation on the single electron and pair densities is investigated for the water molecule.     

Generation of a triplet diradical from a donor-acceptor cross conjugate upon acid-induced electron transfer

Enhancement of the electron acceptor ability of a para-quinodiimine unit by double protonation leads to the proton-induced intramolecular electron transfer from the donor unit to the cross-conjugated acceptor, giving rise to ground state triplet diradical reversibly.     

Transient photocurrents in a charge transfer complex of trinitrofluorenone with a carbazole substituted discotic liquid crystal

We describe transient photoconduction studies on a well known triphenylene discotic liquid crystal molecule modified to incorporate a single carbazole moiety on one side chain and doped with the acceptor, trinitrofluorenone. This material is found to show both electron and hole photocurrents when the transient photoconduction study is carried out in the time of flight geometry although no time of flight transits are observed. Of interest here is the fact that the temperature dependence of the hole and electron photocurrents are radically different, the electron photocurrent being strongly activated while the hole photocurrent decreases with increasing temperature. We suggest a mechanism whereby the electron photocurrent controls the hole photocurrent through recombination. Furthermore, the electron activation energy varies with the applied electric field, indicating the influence of the Poole Frenkel barrier lowering mechanism in the production of the charge carriers.     

Photoinduced electron transfer between a donor and an acceptor separated by a capsular wall

The efficient photoinduced electron transfer from a stilbene derivative incarcerated within a negatively charged organic nanocapsule to positively charged acceptors (methyl viologen and a pyridinium salt) adsorbed outside and the back electron transfer were controlled by supramolecular effects.     

Effect of dimensionality of a crystal lattice on the properties of a localized impurity

The changes of electron density due to the presence of a localized impurity in a crystal lattice are examined in dependence on the lattice dimensionality. The Koster–Slater impurity model developed for the case of a three-dimensional simple cubic lattice has been taken as the basis of examinations. Ordinary bound states, virtual bound states, and delocalized electron states are considered in each lattice case. For the delocalized states extended in a one-dimensional lattice the amplitude of the oscillatory changes of the electron density due to the impurity perturbation does not decrease with the distance from the impurity position, whereas for a two-dimensional lattice this amplitude decreases roughly proportionally to the reciprocal value of the square root of the distance from the impurity. Let us note that a well-known amplitude characterizing the decrease of the oscillatory change of the electron density in a three-dimensional system is proportional to the reciprocal value of the third power of the distance from the impurity position. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 79: 57–74, 2000     

Electron Transfer in a Supramolecular Associate of a Fullerene Fragment

Herein, we investigate the association of a fullerene fragment, hemifullerene C₃₀H₁₂, with an electron‐donating bowl‐shaped tetrathiafulvalene derivative (truxTTF). UV/Vis titrations and DFT calculations support formation of the supramolecular complex, for which an association constant of log K_a=3.6±0.3 in CHCl₃ at room temperature is calculated. Remarkably, electron transfer from truxTTF to C₃₀H₁₂ to form the fully charge‐separated species takes place upon irradiation of the associate with light, constituting the first example in which a fullerene fragment mimics the electron‐accepting behavior of fullerenes within a supramolecular complex.     

Control of Electron Density and Temperature with a Modified Capacitive Discharge

We propose a new type of capacitive plasma source with a mesh grid to solve the problems of previous low pressure discharges, the inability to control the electron density and temperature independently, i.e. just one value of electron temperature is possible for a given electron density. While varying the grid bias and the discharge current, various electron temperatures are possible for a given electron density, and the electron density and temperature can be controlled from 4 × 10⁸ cm^-3 to 1 × 10¹⁰cm^-3 and from 1 to 4 eV, respectively.     

Effect of dimensionality of a crystal lattice on the properties of a localized impurity

The changes of electron density due to the presence of a localized impurity in a crystal lattice are examined in dependence on the lattice dimensionality. The Koster–Slater impurity model developed for the case of a three‐dimensional simple cubic lattice has been taken as the basis of examinations. Ordinary bound states, virtual bound states, and delocalized electron states are considered in each lattice case. For the delocalized states extended in a one‐dimensional lattice the amplitude of the oscillatory changes of the electron density due to the impurity perturbation does not decrease with the distance from the impurity position, whereas for a two‐dimensional lattice this amplitude decreases roughly proportionally to the reciprocal value of the square root of the distance from the impurity. Let us note that a well‐known amplitude characterizing the decrease of the oscillatory change of the electron density in a three‐dimensional system is proportional to the reciprocal value of the third power of the distance from the impurity position. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 80: 61–78, 2000     

Solid-state electron transport across azurin: from a temperature-independent to a temperature-activated mechanism

The temperature dependence of current-voltage values of electron transport through proteins integrated into a solid-state junction has been investigated. These measurements were performed from 80 up to 400 K [above the denaturation temperature of azurin (Az)] using Si/Az/Au junctions that we have described previously. The current across the ～3.5 nm thick Az junction was temperature-independent over the complete range. In marked contrast, for both Zn-substituted and apo-Az (i.e., Cu-depleted Az), thermally activated behavior was observed. These striking temperature-dependence differences are ascribed to the pivotal function of the Cu ion as a redox center in the solid-state electron transport process. Thus, while Cu enabled temperature-independent electron transport, upon its removal the polypeptide was capable only of supporting thermally activated transport.     

Determination of End-to-End Distances in a Series of TEMPO Diradicals of up to 2.8 nm Length with a New Four-Pulse Double Electron Electron Resonance Experiment

A four-pulse version of the pulsed double electron electron resonance (DEER) experiment has been applied to a series of TEMPO diradicals with well-defined interradical distances ranging from 1.4 to 2.8 nm (see picture). The new pulse sequence allows broad distributions of electron–electron distances to be measured without dead-time artifacts.     

Topological analysis of electron density distribution taken from a pseudopotential calculation

Theoretical studies of the electron density topology at the bond critical point for some small molecules, Ti, and Mo organometallic complexes were undertaken in order to understand the reason for the failure of the topological analysis of the coreless electron densities obtained from a pseudopotential calculation. We show that the absence of the core electron density is the main reason for such behavior. The erratic behavior of the effective core potentials electron densities can be corrected by adding atomic electron core density obtained from a single-atom Hartree-Fock calculation. The effect of orthogonalization of the core orbital with the valence orbitals was also investigated. © 1997 by John Wiley & Sons, Inc.     

Ammoniated electron as a solvent stabilized multimer radical anion

The excess electron in liquid ammonia ("ammoniated electron") is commonly viewed as a cavity electron in which the s-type wave function fills the interstitial void between 6 and 9 ammonia molecules. Here we examine an alternative model in which the ammoniated electron is regarded as a solvent stabilized multimer radical anion in which most of the excess electron density resides in the frontier orbitals of N atoms in the ammonia molecules forming the solvation cavity. The cavity is formed due to the repulsion between negatively charged solvent molecules. Using density functional theory calculations, we demonstrate that such core anions would semiquantitatively account for the observed pattern of Knight shifts for 1H and 14N nuclei observed by NMR spectroscopy and the downshifted stretching and bending modes observed by infrared spectroscopy. We speculate that the excess electrons in other aprotic solvents might be, in this respect, analogous to the ammoniated electron, with substantial transfer of the spin density into the frontier N and C orbitals of methyl, amino, and amide groups.     

Molecular geometry and symmetry from a differential geometry viewpoint

Relations between an earlier generalization of molecular symmetry called symmorphy and a molecular equivalence based on diffeomorphisms of electron density functional graphs (the so-called DFG equivalence introduced in our previous work) are analyzed. Any two DFG-equivalent electron density functions can be derived from one another by a suitable transformation of the spatial coordinates and the electronic charge density scale; the classes of DFG equivalence are the orbits of a group of linear operators operating in the space of electron density functions. Within the symmorphy framework, the symmetry group is derived from the symmorphy group by taking an intersection of a subgroup of the symmorphy group and the group of isometries for a natural choice of the Riemannian metric tensor. The Riemannian metric properties provide a choice for a suitable reference electron density function for each class of equivalent densities. Such reference densities serve as tools for a systematic classification of the infinite family of electron densities of molecular conformations. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 64 : 669–678, 1997