MECHANISM OF ORIENTATION AND LINEAR DICHROISM OF PHOTOSYNTHETIC PARTICLES IN ELECTRIC FIELDS: CHLOROPLASTS AND CHLOROPHYLL-PROTEIN COMPLEXES

Abstract— The mechanisms of orientation in pulsed and alternating electric fields of thylakoids (derived from the sonication of spinach chloroplasts) and of light-harvesting chlorophyll a/b-protein complexes (CPII) were investigated by utilizing linear dichroism techniques. Comparisons of the linear dichroism spectra of thylakoids and CPII particles suggest that the latter are oriented with their directions of largest electronic polarizabilities (and thus probably their largest dimensions) within the thylakoid membrane planes. At low electric field strengths (< 12 V cm^?1), and at low frequencies of alternating electric fields (< 0.25 Hz), thylakoid membranes tend to align with their normals parallel to the direction of the applied electric field; the mechanism of orientation involves a permanent dipole moment of the thylakoids which is oriented perpendicular to the planes of the membranes. However, at high field strengths and high frequencies of the applied alternating electric fields, the thylakoids tend to orient with their planes parallel to the applied field, thus exhibiting an inversion of the sign of the linear dichroism as the electric field strength is increased. At the higher frequencies and at higher field strengths, the orientation mechanisms of the thylakoids involve induced dipole moments related to anisotropies in the electronic polarizabilities. The polarizability is higher within the plane than along a normal to the plane, thus accounting for the inversion of the dichroism as the electric field strength is increased. The CPII particles align with their largest dimension parallel to the applied field at all field strength, indicating that the induced dipole moment dominates the orientation mechanisms in pulsed electric fields. The magnitude of the absolute linear dichroism of CPII suspensions increases with increasing dilution, indicating that aggregates of lower symmetry are formed at higher concentrations of the CPII complexes.     

Dynamics of molecules in strong oscillating electric fields using time-dependent Hartree-Fock theory

Restricted and unrestricted forms of time-dependent Hartree-Fock theory have been implemented and used to study the electronic dynamics of ethene, benzene, and the formaldehyde cation subjected to both weak and strong oscillating electric fields. Absorption spectra and frequency-dependent polarizabilities are calculated via the instantaneous dipole moment and its derivative. In the weak field limit the computed excitation energies agree very well with those obtained using linearized time-dependent Hartree-Fock theory, which is valid only in the low-field perturbation limit. For strong fields the spectra show higher-order excitations, and a shift in the position of the excitations, which is due to the nonadiabatic response of the molecules to the field. For open-shell systems in the presence of strong oscillating electric fields, unrestricted time-dependent Hartree-Fock theory predicts the value of S(2) to vary strongly with time.     

Calculation of direct and indirect excitons in GaAs–Ga1−xAlxAs coupled double quantum wells: Electric and magnetic fields and hydrostatic pressure effects

A study of the electronic and optical properties of coupled double quantum wells is presented. Within the framework of the effective mass and parabolic-band approximations we have calculated the electron–hole and photoluminescence energy transitions under simultaneous effects of electric and magnetic fields. For that purpose, a variational procedure has been used, taking into account the effect of hydrostatic pressure. The electric field is taken to be oriented along the growth direction of the heterostructure whereas for the magnetic field both in-plane and in-growth directions have been considered. The results show that hydrostatic pressure is a useful tool to tune the direct and indirect exciton transitions in such heterostructures. It is shown that the photoluminescence peak energy transitions strongly depend on the external fields and hydrostatic pressure studied here. Furthermore, our numerical outcome is in good agreement with previous experimental findings at zero pressure in double quantum wells under applied electric and magnetic fields.     

Efficient vector potential method for calculating electronic and nuclear response of infinite periodic systems to finite electric fields

The response of periodic systems to external electric fields is a challenging theoretical problem. The authors show how the vector potential approach yields a numerically efficient treatment of the combined electronic and nuclear response to a finite static field. Their method is based on a self-consistent reformulation of the charge flow term in the single particle Hamiltonian. Careful numerical implementation yields a treatment whose computational needs are only marginally larger than those of a conventional field-free calculation. To prove the method exemplary polymer calculations are done for a model Hamiltonian. The latter contains all essential elements of an ab initio Kohn-Sham or Hartree-Fock Hamiltonian but allows for extensive testing. The extension to three-dimensional systems is described.     

A numerical simulation of nonadiabatic electron excitation in the strong field regime: Linear polyenes

Time-dependent Hartree-Fock theory has been used to study of the electronic optical response of a series of linear polyenes in strong laser fields. Ethylene, butadiene, and hexatriene have been calculated with 6-31G(d,p) in the presence of a field corresponding to 8.75 x 10(13) W/cm2 and 760 nm. Time evolution of the electron population indicates not only the pi electrons, but also lower lying valence electrons are involved in electronic response. When the field is aligned with the long axis of the molecule, L?wdin population analysis shows large charges at each end of the molecule. For ethylene, the instantaneous dipole moment followed the field adiabatically, but for hexatriene, nonadiabatic effects were very pronounced. For constant intensity, the nonadiabatic effects in the charge distribution, instantaneous dipole, and orbital populations increased nonlinearly with the length of the polyene. These calculations elucidate the mechanism of the strong field nonadiabatic electron excitation of polyatomic molecules leading to their eventual ionization and fragmentation. The described computational methods are a viable tool for studying the complex processes in multielectron atomic and molecular systems in strong laser fields.     

Mono- and bichromatic electron dynamics: LiH, a test case

This paper describes an electron dynamics method where the time dependence of an external oscillating electric field is the perturbing part of the Hamiltonian. Application of the electric field induces charge movement inside the molecule and electronic transitions between the molecular orbitals. The test system is the neutral LiH molecule. The method is applied to wave functions calculated using the B3LYP (hybrid) density functional, with the STO-3G and the 6-31+G basis sets. The molecule undergoes full population inversion between the HOMO and the LUMO when the electric field is in resonance with the HOMO-LUMO energy gap. The magnitude of the electric field directly affects the rate at which electronic transitions occur and the rate at which charges move between lithium and hydrogen atoms. The method is used to model both monochromatic and bichromatic multiphoton effects in LiH. Monochromatic one-, two- and three-photon transitions occur between the HOMO, LUMO and two other virtual orbitals. There is evidence of both [1+2] direct and [1+1+1] stepwise multiphoton transitions. Bichromatically, two "laser" pulses are applied at different frequencies. Electronic transitions can be fine-tuned to occur via pre-specified pathways of virtual molecular orbitals.     

Theoretical study of electric field‐induced intramolecular electron transfer in donor–acceptor pairs via the rigid space and their suitability as molecular electronic devices

The geometries of two reaction systems have been optimized under the constraint of C_2ν symmetry, using the UHF/6‐31G method. The potential energy surfaces (PES) of the two systems in different external electric field have been constructed using a linear reaction coordinate. It is concluded that the reorganization energies and electron transfer matrix elements for both systems are almost independent of the external electric field. However, the standard Gibbs energy difference changes remarkably with the change of the external electric field. Hence, the applied electric field leads to the variation of rate constant of electron transfer reaction. The threshold field, where the electron transfer becomes barrier free, is obtained to be 0.0015 a.u. for the anion system 1, and 0.00097 a.u. for the anion system 2. The threshold field for modified system 1, in which the hydrogen atoms linking to benzene rings are replaced by fluorine atom, is 0.0018 a.u. The calculations show that the best way to adjust the threshold field is to adjust the dipole moment of the reaction system by changing the length of the bridge. As the rate constant in field‐free case is taken into account, neither reaction systems could be used as molecular electronic device. But if the bridge consists of three or four HCTDs, the rate constant and threshold field will satisfy the practical demand. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

PHOTOSENSITIZATION OF CONDUCTION IN MOLECULAR SOLIDS*

Abstract— The mechanism of spectral sensitization of conduction in molecular photoconductors has been investigated in systems in which sensitizer and photoconductor form separate layers. The efficiency of sensitization is strongly influenced by external fields, approaching 100 per cent at 10⁶ V/cm in certain cases. The spectral response, efficiency, and field dependence are characteristic primarily of the sensitizer, while the transport characteristics are largely determined by the photoconductor. These results are considered in the light of available information concerning the molecular energy levels of the materials studied. They support the view that light absorption produces mobile electronic charge carriers in the sensitizer, which may be separated, injected, and transported across the photoconductor under an applied electric field. This mechanism is consistent with the interpretation of work on electrolyte-photoconductor contacts, and appears to account for all that is presently known about optical sensitization of molecularly bonded photoconductors.     

Carbon nanotubes films: electronic properties and their application as field emitters

Aligned carbon nanotube films have been studied with a wide variety of characterization techniques. Although nanotubes resemble bulk graphite as far as carrier densities, susceptibilities and conductivities are concerned, transport properties and ESR measurments indicate that carrier localization occurs at low temperatures. Nanotube films are good field emitters producing large currents at relatively low electric fields. The performance is superior to the intensely studied CVD diamond films in particular for the threshold field for electron emission. We believe that the observed remarkable electron emission is related to the special electronic structure of the nanotube tips.     

Manipulating Metal‐to‐Metal Charge Transfer for Materials with Switchable Functionality

Metal‐to‐metal charge transfer (MMCT) describes electron transfer between metal ions, to generate valence isomers with markedly different electronic configurations. In particular, MMCT changes the spin states of single‐metal sites and the coupling interactions between them, while also changing the symmetry in charge distribution. The result is a drastic change in both magnetic and electric properties of the affected material. Moreover, MMCT causes significant variation in bond length and absorption spectra, and induces unusual thermal expansion and photochromic behavior. Thus, materials demonstrating MMCT in response to external stimuli are excellent candidates for switchable multifunctional devices with synergistic responses. In this Minireview, recent progress in utilizing MMCT units as actuators to tune magnetic, electric, thermal expansion, and photochromic properties in cyanide‐bridged systems is highlighted, and emphasis is given to the remaining challenges and future perspectives in the field.     

Deformation of magnetosensitive emulsion microdroplets in magnetic and electric fields

A magnetosensitive emulsion comprising an ensemble of nonmagnetic oil droplets suspended in a kerosene-based magnetic fluid is studied. It is found that the droplets of such an emulsion are deformed in both magnetic and electric fields. The character of microdroplet deformation in the electric field depends on the field frequency: at low frequencies, the droplets are flattened; at high frequencies, the droplets are stretched along the force lines of the field. It is established that the deformation caused by the electric field can be compensated for by the imposition of an additional magnetic field, and the conditions of this compensation are determined. It is revealed that, under the action of a magnetic field directed normal to a thin layer of the emulsion, the droplets “split” into branched structures. The action of a similarly directed alternating electric field leads to the transformation of the droplets into tori followed by their rupture. It is concluded that the structure of the emulsion can be efficiently controlled using the combined action of magnetic and electric fields. Original Russian Text ? Yu.I. Dikanskii, O.A. Nechaeva, A.R. Zakinyan, 2006, published in Kolloidnyi Zhurnal, 2006, Vol. 68, No. 2, pp. 161–165.     

Molecular binding at gold transport interfaces. III. Field dependence of electronic properties

The behavior of the electronic structure in a metal/molecular/metal junction as a function of the applied electric field is studied using density functional methods. Although the calculations reported here do not include the electrode bulk, or intermolecular interactions, and do not permit actual transport to occur, nevertheless they illuminate the charging, energy shift, polarization and orbital occupation changes in the molecular junction upon the application of a static electric field. Specifically, external electric fields generally induce polarization localization on the two cluster ends. The HOMO/LUMO gap usually decreases and, for large enough fields, energy levels can cross, which presages a change of electronic state and, if found in molecular electronic circuits, a change in transmission. The calculations also show changes in the geometry both of the molecule and the molecule/cluster interface upon application of the electric field. These effects should be anticipated in whole circuit studies.     

The role of electrode impedance and electrode geometry in the design of microelectrode systems

Microelectromechanical systems (MEMS) employing spatially and/or temporally nonuniform electric fields have been extensively employed to control the motion of suspended particles or fluid flow. Design and control of microelectromechanical processes require accurate calculations of the electric field distribution under varying electrolyte conditions. Polarization of electrodes under the application of an oscillating voltage difference produces dynamic electrical double layers. The capacitive nature of the double layers significantly inhibits the penetration of the electric field through the double layer and into the surrounding bulk electrolyte at low frequencies. This paper quantitatively discusses the effect of electrode impedance on the electric field distribution as a function of field frequency, electrolyte composition, and electrode zeta potential in microelectrode systems. The design principles for the electrode geometry and configuration are also discussed in terms of their effects on the electric field magnitude and nonuniformity.     

非水介质中明胶水凝胶电场驱动行为的研究

研究了明胶水凝胶在绝缘硅油中的电场响应行为。结果表明,在硅油中,明胶水凝胶在外加高压直流电场作用下可发生运动,其运动由转动和平动两部分组成。存在一个运动所需的最小阈值电场,只有外加电场在此阈值以上时,才可观察到水凝胶明显的运动。水凝胶的运动速度随外加电场的增大而增大,其运动可通过外加电场的大小来调控。由硅油很稳定且在电场中会电解,因此避免了传统电场驱动水凝胶在水介质中响应时不可避免的电解缺点,为建立一种新的电响应凝毅然驱动方式提供了可能。     

Nonmonotonous variation of DNA angular separation during asymmetric pulsed field electrophoresis

Asymmetric pulsed field electrophoresis within crystalline arrays is used to generate angular separation of DNA molecules. Four regimes of the frequency response are observed, a low frequency rise in angular separation, a plateau, a subsequent decline, and a second plateau at higher frequencies. It is shown that the frequency response for different sized DNA is governed by the relation between pulse time and the reorientation time of DNA molecules. The decline in angular separation at higher frequencies has not previously been analyzed. Real‐time videos of single DNA molecules migrating under high frequency‐pulsed electric field show the molecules no longer follow the head to tail switching, ratchet mechanism seen at lower frequencies. Once the pulse period is shorter than the reorientation time, the migration mechanism changes significantly. The molecule reptates along the average direction of the two electric fields, which reduces the angular separation. A freely jointed chain model of DNA is developed where the porous structure is represented with a hexagonal array of obstacles. The model qualitatively predicts the variation of DNA angular separation with respect to frequency.     

Conductivity of molten sodium chloride in an arbitrarily weak dc electric field

We use nonequilibrium molecular-dynamics (NEMD) simulations to characterize the response of a fluid subjected to an electric field. We focus on the response for very weak fields. Fields accessible by conventional NEMD methods are typically of the order of 10(9) V m(-1), i.e., several orders of magnitude larger than those typically used in experiments. Using the transient time-correlation function, we show how NEMD simulations can be extended to study systems subjected to a realistic dc electric field. We then apply this approach to study the response of molten sodium chloride for a wide range of dc electric fields.     

Control of delocalization and structural changes by means of an electric field

The strength and, mainly, the direction of a static electric field can be used to control delocalization effects occurring in a non-polar pi-system. The delocalization energy, the weights, and the probabilities of some local electronic structures, the behavior of electron pairs, and the electronic fluctuations are considered and examined in cis-butadiene, used as model system. The effects of the electric field are detected and evaluated in the basis of natural orbital spaces appropriate to investigate the behavior of one- and poly-electron distributions. The consequences of modifying the delocalization effects on structural changes are also investigated. Full geometry optimizations in both Hartree-Fock and MP2 levels show that the changes in bond lengths, guided by the changes of the behavior of the electronic assembly, can be controlled by means of the electric field.     

QM:QM embedding using electronic densities within an ONIOM framework: energies and analytic gradients

Accurate calculations of large systems remain a challenge in electronic structure theory. Hybrid energy techniques are a promising family of methods for treating such systems. Expanding on previous developments, we present a QM:QM electronic embedding model whereby the high-level region is polarized by the electron density of the low-level region within an ONIOM framework. A direct Coulomb embedding model as well a more computationally efficient model involving a density fitting expansion are considered. We also develop a generalized theory for the first derivatives of these classes of QM:QM electronic embedding schemes, which requires solution of a single set of self-consistent field response equations. Two initial test cases are presented and discussed.