Charge Migration Process Research Articles

The AT Interstrand Cross-Link: Structure, Electronic Properties, and Influence on Charge Transfer in dsDNA

The interaction of chemical and physical agents with genetic material can lead to almost 80 different DNA damage formations. The targeted intentional DNA damage by radiotherapy or chemotherapy is a front-line anticancer therapy. An interstrand cross-link can result from ionization radiation or specific chemical agents, such as trans-/cisplatin activity. Here, the influence of the adenine and thymidine (AT) interstrand linkage, the covalent bond between the adenine N6 and thymidine C5 methylene group, on the isolated base pair as well as double-stranded DNA (dsDNA) was taken into quantum mechanical/molecular mechanical (QM/MM) consideration at the m062x/6-31+G*:UFF level of theory in the aqueous phase. All the results presented in this article, for the first time, show that an AT-interstrand cross-link (ICL) changes the positive and negative charge migration process due to a higher activation energy forced by the cross-link’s presence. However, the final radical cation destination in cross-linked DNA is left in the same place as in a native double-stranded-deoxyoligonucleotide. Additionally, the direction of the radical anion transfer was found to be opposite to that of native dsDNA. Therefore, it can be postulated that the appearance of the AT-ICL does not disturb the hole migration in the double helix, with subsequent effective changes in the electron migration process.

Real-time dynamics of Auger wave packets and decays in ultrafast charge migration processes

The Auger decay is a relevant recombination channel during the first few femtoseconds of molecular targets impinged by attosecond XUV or soft X-ray pulses. Including this mechanism in time--dependent simulations of charge--migration processes is a difficult task, and Auger scatterings are often ignored altogether. In this work we present an advance of the current state-of-the-art by putting forward a real--time approach based on nonequilibrium Green's functions suitable for first-principles calculations of molecules with tens of active electrons. To demonstrate the accuracy of the method we report comparisons against accurate grid simulations of one-dimensional systems. We also predict a highly asymmetric profile of the Auger wavepacket, with a long tail exhibiting ripples temporally spaced by the inverse of the Auger energy.

Ultrafast Charge Migration in XUV Photoexcited Phenylalanine: A First-Principles Study Based on Real-Time Nonequilibrium Green's Functions.

The early-stage density oscillations of the electronic charge in molecules irradiated by an attosecond XUV pulse takes place on femto- or subfemtosecond time scales. This ultrafast charge migration process is a central topic in attoscience because it dictates the relaxation pathways of the molecular structure. A predictive quantum theory of ultrafast charge migration should incorporate the atomistic details of the molecule, electronic correlations, and the multitude of ionization channels activated by the broad-bandwidth XUV pulse. We propose a first-principles nonequilibrium Green's function method fulfilling all three requirements and apply it to a recent experiment on the photoexcited phenylalanine amino acid. Our results show that dynamical correlations are necessary for a quantitative overall agreement with the experimental data. In particular, we are able to capture the transient oscillations at frequencies 0.15 and 0.30 PHz in the hole density of the amine group as well as their suppression and the concomitant development of a new oscillation at frequency 0.25 PHz after ∼14 fs.

(Invited) Correlation of Charge Carrier Behaviors with Band Structure of Semiconductor-Based Photocatalysts

This presentation will discuss the correlation of band structure with charge separation, charge migration and charge recombination in the semiconductor-based photocatalysts. Doping elements into the semiconductor could alter the electronic band structure, which will change the charge separation and charge recombination processes, leading to modulation of photocatalytic activity. When two materials are formed to a heterojunction, the band alignment and the interfacial defects in the heterojunction have significant effects on the charge separation, charge migration and charge recombination processes.

An open-source framework for analyzing N-electron dynamics. II. Hybrid density functional theory/configuration interaction methodology.

In this contribution, we extend our framework for analyzing and visualizing correlated many-electron dynamics to non-variational, highly scalable electronic structure method. Specifically, an explicitly time-dependent electronic wave packet is written as a linear combination of N-electron wave functions at the configuration interaction singles (CIS) level, which are obtained from a reference time-dependent density functional theory (TDDFT) calculation. The procedure is implemented in the open-source Python program detCI@ORBKIT, which extends the capabilities of our recently published post-processing toolbox (Hermann et al., J. Comput. Chem. 2016, 37, 1511). From the output of standard quantum chemistry packages using atom-centered Gaussian-type basis functions, the framework exploits the multideterminental structure of the hybrid TDDFT/CIS wave packet to compute fundamental one-electron quantities such as difference electronic densities, transient electronic flux densities, and transition dipole moments. The hybrid scheme is benchmarked against wave function data for the laser-driven state selective excitation in LiH. It is shown that all features of the electron dynamics are in good quantitative agreement with the higher-level method provided a judicious choice of functional is made. Broadband excitation of a medium-sized organic chromophore further demonstrates the scalability of the method. In addition, the time-dependent flux densities unravel the mechanistic details of the simulated charge migration process at a glance. © 2017 Wiley Periodicals, Inc.

An open-source framework for analyzing N-electron dynamics. I. Multideterminantal wave functions.

The aim of the present contribution is to provide a framework for analyzing and visualizing the correlated many-electron dynamics of molecular systems, where an explicitly time-dependent electronic wave packet is represented as a linear combination of N-electron wave functions. The central quantity of interest is the electronic flux density, which contains all information about the transient electronic density, the associated phase, and their temporal evolution. It is computed from the associated one-electron operator by reducing the multideterminantal, many-electron wave packet using the Slater-Condon rules. Here, we introduce a general tool for post-processing multideterminant configuration-interaction wave functions obtained at various levels of theory. It is tailored to extract directly the data from the output of standard quantum chemistry packages using atom-centered Gaussian-type basis functions. The procedure is implemented in the open-source Python program detCI@ORBKIT, which shares and builds on the modular design of our recently published post-processing toolbox (Hermann et al., J. Comput. Chem. 2016, 37, 1511). The new procedure is applied to ultrafast charge migration processes in different molecular systems, demonstrating its broad applicability. Convergence of the N-electron dynamics with respect to the electronic structure theory level and basis set size is investigated. This provides an assessment of the robustness of qualitative and quantitative statements that can be made concerning dynamical features observed in charge migration simulations. © 2017 Wiley Periodicals, Inc.

Quantum control with smoothly varying pulses: general theory and application to charge migration

Using direct search algorithms for solving the quantum optimization problem, we demonstrate on model systems that with specifically tailored Gaussian-form laser pulses one can achieve a very good control over the dynamics in complicated quantum systems. We show that by manipulating a very limited number of laser-pulse parameters, one is able to control the charge migration process in molecules. In particular, by combining two identical Gaussian laser pulses with an appropriate delay between them, one can stop the pure electronic, few-femtosecond oscillation of the charge, redistributing it along the molecule of propiolic acid.

Ultrafast charge dynamics in glycine induced by attosecond pulses

The combination of attosecond pump-probe techniques with mass spectrometry methods has recently led to the first experimental demonstration of ultrafast charge dynamics in a biomolecule, the amino acid phenylalanine [Calegari et al., Science, 2014, 346, 336]. Using an extension of the static-exchange density functional theory (DFT) method, the observed dynamics was explained as resulting from the coherent superposition of ionic states produced by the broadband attosecond pulse. Here, we have used the static-exchange DFT method to investigate charge migration induced by attosecond pulses in the glycine molecule. We show that the observed dynamics follows patterns similar to those previously found in phenylalanine, namely that charge fluctuations occur all over the molecule and that they can be explained in terms of a few typical frequencies of the system. We have checked the validity of our approach by explicitly comparing with the photoelectron spectra obtained in synchrotron radiation experiments and with the charge dynamics that follows the removal of an electron from a given molecular orbital, for which fully correlated ab initio results are available in the literature. From this comparison, we conclude that our method provides an accurate description of both the coherent superposition of cationic states generated by the attosecond pulse and its subsequent time evolution. Hence, we expect that the static-exchange DFT method should perform equally well for other medium-size and large molecules, for which the use of fully correlated ab initio methods is not possible.

Investigation of charge trapping and detrapping dynamics in LDPE, HDPE and XLPE

In this paper, charge trapping and detrapping dynamics of PE-based materials, i.e., LDPE, HDPE, XLPE were investigated by isothermal surface potential decay method (ISPD). The whole charge transport process including ions generation process in the air, charge trapping in the top surface, the surface potential establishing process, the charge migration process in the bulk was considered in these PE-based materials. The results showed that the trapping process was closely related to the capture cross section, the injected carrier concentration and the trap level. The established surface potential was mainly determined by the captured carriers in the top surface of the PE-based materials. In addition, it was found that the mobility of LDPE was much larger than that of XLPE and HDPE. And it is shown that deep traps may play a more important role in the charge migration process than shallow traps in these PE-based materials. It is indicated that the discrepancy of charge trapping and detrapping dynamics between these PE-based materials may be attributed to the different microscopic morphology.

Ultrafast photoelectron migration in dye-sensitized solar cells: Influence of the binding mode and many-body interactions.

In the present contribution, the ultrafast photoinduced electron migration dynamics at the interface between an alizarin dye and an anatase TiO2 thin film is investigated from first principles. Comparison between a time-dependent many-electron configuration interaction ansatz and a single active electron approach sheds light on the importance of many-body effects, stemming from uniquely defined initial conditions prior to photoexcitation. Particular emphasis is put on understanding the influence of the binding mode on the migration process. The dynamics is analyzed on the basis of a recently introduced toolset in the form of electron yields, electronic fluxes, and flux densities, to reveal microscopic details of the electron migration mechanism. From the many-body perspective, insight into the nature of electron-electron and hole-hole interactions during the charge transfer process is obtained. The present results reveal that the single active electron approach yields quantitatively and phenomenologically similar results as the many-electron ansatz. Furthermore, the charge migration processes in the dye-TiO2 model clusters with different binding modes exhibit similar mechanistic pathways but on largely different time scales.

Space charge characteristics of power cables under AC stress and temperature gradients

A pulsed electro-acoustic equipment system was devised to measure the space charge of a power cable under 50 Hz AC stress and a high temperature gradient by adopting a new phase-matching method. Space charge profiles were recorded on a 10 kV cable with cross-linked polyethylene insulation. The AC period was resolved in 32 phase angles, while the cable underwent electrical-thermal aging for 16 days. Two types of space charge were discovered, termed periodic charge and stationary charge according to whether they change with AC phases. The periodic charge was not determined to develop over time, while the stationary charge increased gradually as the cable aged. A method called the all-phase average was employed to clearly recognize the stationary charge. An interesting phenomenon was discovered upon attempting to regenerate space charge in the cable after the charge was eliminated. The stationary charge regeneration speed was found to depend strongly on temperature and electrical field. This paper provides a theoretical interpretation for the generation of periodic charge and stationary charge, as well as the dependence of charge regeneration on temperature and electrical field. A new model is raised to account for the generation of stationary charge, explaining how residual charge in one sine period undergoes different charge migration processes around a tip defect between negative and positive periods.

On the Attosecond charge migration in Cl…..N, Cl…..O, Br…..N and Br…..O Halogen-bonded clusters: Effect of donor, acceptor, vibration, rotation, and electron correlation

The electron-electron relaxation and correlation-driven charge migration process, which features pure electronic aspect of ultrafast charge migration phenomenon, occurs on a very short timescale in ionized molecules and molecular clusters, prior to the onset of nuclear motion. In this article, we have presented nature of ultrafast pure electronic charge migration dynamics through Cl…..N, Cl…..O, Br…..N, and Br…..O halogen bonds, explored using density functional theory. We have explored the role of donor, acceptor, electron correlation, vibration and rotation in charge migration dynamics through these halogen bonds. For this work, we have selected ClF, Cl2, ClOH, ClCN, BrF, BrCl, BrOH, and BrCN molecules paired with either NH3 or H2O. We have found that the timescale for pure electron-electron relaxation and correlation-driven charge migration through the Cl…..N, Br…..N, Cl…..O, and Br…..O halogen bonds falls in the range of 300–600 attosecond. The primary driving force behind the attosecond charge migration through the Cl…..N, Br…..N, Cl…..O, and Br…..O halogen bonds is the energy difference (ΔE) between two stationary cationic orbitals (LUMO- β and HOMO- β), which together represents the initial hole density immediately following vertical ionization. We have also predicted that the strength of electron correlation has significant effect on the charge migration timescale in Cl…..N, Br…..N, Cl…..O, and Br…..O halogen bonded clusters. Vibration and rotation are also found to exhibit profound effect on attosecond charge migration dynamics through halogen bonds. The attosecond charge migration dynamics through Cl…..N, Cl…..O, Br…..N, and Br…..O halogen bonds depends on strength of electron correlation, donor and acceptor, the energy difference (ΔE) between two stationary cationic orbitals (LUMO-β and HOMO-β) involved in electronic superposition, vibration and rotation.

(Invited) The Use of Broadband Electric Spectroscopy to Probe the Relaxations and Polarizations in Phase Seperated Polymer Electrolytes

There has been a recent surge in interest in the use of anion exchange membranes (AEMs) as the separator in many electrochemical conversion devices such as fuel cells, electrolyzers, redox flow cells, and for uses in electrochemical water purification processes. This is because electrocatalysis is generally more facile in alkaline conditions, and so these devices could potentially operate with non-precious metal catalysts and with catalysts capable of oxidizing or generating fuels beyond hydrogen. An AEM with high anionic conductivity would overcome many of the disadvantages of proton exchange membrane devices that need precious metal catalyst and work best with hydrogen. Improved AEMs are also required for water purification applications. Realization of AEM devices, therefore, would revolutionize electrochemical energy conversion, as inexpensive versatile devices could be made available. While much attention has been focused on generating new AEMs with stable cations and backbones, very little attention has been paid to the design of AEMs to maximize ionic conductivity and water transport. The work presented here represents the first detailed study of the thermomechanical, polarization, and dielectric phenomena related to morphology in a series of AEMs. In detail in this presentation, the micro-structure is studied by Small Angle X-ray Scattering (SAXS), the thermal stability and transitions are detected by High-Resolution Thermogravimetry (HR-TG) and by Modulated Differential Scanning Calorimetry (MDSC), respectively. The mechanical properties and transitions are investigated by Dynamic Mechanical Analysis (DMA). Broadband Electrical Spectroscopy (BES) is used to study the electric response and the conductivity mechanisms of the membranes in the frequency and temperature range of 0. 01—107 Hz and -105 — 100 °C, respectively. BES is a powerful technique, which allows us to fully understand the overall electric response and dielectric relaxations of the membranes, both in a completely dry state and after full hydration, thus allowing clarification of the role played by both ion solvation phenomena and water cluster structure on performance of these materials. The integration of the information acquired by the above techniques allows us to propose a reasonable mechanism for the long-range charge migration processes in polyvinylbenzyltrimethylamne bromide-block-polymethylbutylene [PVBTMA][Br]-b-PMB, it hydoxide analogue and the random polymers of the same chemistry crosslinked by UV and thermal methods. We have also extended this study to polyphenylene-b-[PVBTMA][OH] and the pentablock quaternary ammonium functioalized analogue of the sulfonated polymer, Nexar. In amny of these polymers we observe an order-disorder transition, Tδ, where dispersed cations aglomorate due to the interactions of their dipoles. As Tδ often occurs above 0°C this phenomenom is of nterset to the development of practical devices. This study has important consequences for the design of next generation revolutionary AEMs.

Controllable synthesis of Ag@TiO2 heterostructures with enhanced photocatalytic activities under UV and visible excitation

The proposed mechanism of photo-generated charge separation and migration process in the Ag/TiO2 nanoheterostructures under UV light.

Ultrafast Charge Dynamics in an Amino Acid Induced by Attosecond Pulses

In the past few years, attosecond techniques have been implemented for the investigation of ultrafast dynamics in molecules. The generation of isolated attosecond pulses characterized by a relatively high photon flux has opened up new possibilities in the study of molecular dynamics. In this paper, we report on experimental and theoretical results of ultrafast charge dynamics in a biochemically relevant molecule, namely, the amino acid phenylalanine. The data represent the first experimental demonstration of the generation and observation of a charge migration process in a complex molecule, where electron dynamics precede nuclear motion. The application of attosecond technology to the investigation of electron dynamics in biologically relevant molecules represents a multidisciplinary work, which can open new research frontiers: those in which few-femtosecond and even subfemtosecond electron processes determine the fate of biomolecules. It can also open new perspectives for the development of new technologies, for example, in molecular electronics, where electron processes on an ultrafast temporal scale are essential to trigger and control the electron current on the scale of the molecule.

Electronic Band Structure and Charge Transfer in Semiconductors

Semiconductor has been widely used in photocatalytic and photovoltaic devices. The electronic band structure governs the charge separation, charge migration and charge recombination processes. This talk provides an insight into the band gap, the deep and shallow level states in the band gap and the surface trap states that play important roles in the processes of photo-generated charge carriers in the metal oxide semiconductors. Also, this talk demonstrates how to engineer the bulk band structure and the surface states in order to enhance the solar energy conversion.

Pyrolysis mechanism and electrical properties of 3D-hybrid organic–inorganic materials based on zirconium oxides-hydroxides, 3-butenoates and vinyltrimethoxysilane

This report is focused on the quantitative thermogravimetric–mass spectrometric (TG–MS) analyses and the electrical response of two hybrid organic–inorganic materials (HYP and HYPC), obtained reacting together nanoclusters of zirconium oxides-hydroxides with 3-butenoates and cross-linked with vinyltrimethoxysilane. HYP was cured at 363 K, while HYPC at 403 K. Condensation of the silanol groups, producing shrinkage, alcoholation and the release of 3-butenoic acid and methyl 3-butenoate are the main processes involved in the early stages of pyrolysis from 323 to 633 K. The nominal formula for the two samples with a fair degree of approximation was obtained by elemental analysis and quantitative TG–MS measurements. Morphology of HYP and HYPC is determined by high-resolution transmission electron microscopy. In both HYP and HYPC, the electric response is characterized by a molecular dipole relaxation detected at higher frequencies and an inter-domain polarization phenomenon revealed at the lower frequencies, due to the presence of charged interfaces between nanodomains with different permittivities. HYP material showed a further dipole relaxation at intermediate frequencies, which assists the charge migration process. HYPC, containing a smaller density of 3-butenoate groups, reveals a long-range charge migration event of mobile species by hopping processes between relatively stiff sites.

Electrochemical performance of BaZr0.1Ce0.7Y0.1Yb0.1O3−δ electrolyte based proton-conducting SOFC solid oxide fuel cell with layered perovskite PrBaCo2O5+δ cathode

BaZr0.1Ce0.7Y0.1Yb0.1O3−δ (BZCYYb) exhibits adequate protonic conductivity as well as sufficient chemical and thermal stability over a wide range of SOFC operating conditions, while layered perovskite PrBaCo2O5+δ (PBCO) has advanced electrochemical properties. This research fully takes advantage of these advanced properties and develops a novel protonic ceramic membrane fuel cell (PCMFC) of Ni–BZCYYb|BZCYYb|PBCO. The performance of the button cell was tested under intermediate-temperature range from 600 to 700°C with humified H2 (∼3% H2O) as fuel and ambient air as oxidant. The results show that the open circuit potential of 0.983V and the maximal power density of 490mWcm−2 were achieved at 700°C. By co-doping barium zirconate–cerate with Y and Yb, the conductivity of electrolyte was significantly improved. The polarization processes of the button cell were characterized using the complicated electrochemical impedance spectroscopy technique. The results indicate that the polarization resistances contributed from both charge migration processes and mass transfer processes increase with decreasing cell voltage loads. However the polarization resistance induced by mass transfer processes is negligible in the studied button cell.

Theoretical Characterization of Charge Transport in One‐Dimensional Collinear Arrays of Organic Conjugated Molecules

A great deal of interest has recently focused on host-guest systems consisting of one-dimensional collinear arrays of conjugated molecules encapsulated in the channels of organic or inorganic matrices. Such architectures allow for controlled charge and energy migration processes between the interacting guest molecules and are thus attractive in the field of organic electronics. In this context, we characterize here at a quantum-chemical level the molecular parameters governing charge transport in the hopping regime in 1D arrays built with different types of molecules. We investigate the influence of several parameters (such as the symmetry of the molecule, the presence of terminal substituents, and the molecular size) and define on that basis the molecular features required to maximize the charge carrier mobility within the channels. In particular, we demonstrate that a strong localization of the molecular orbitals in push-pull compounds is generally detrimental to the charge transport properties.

Theoretical description of charge migration with a single Slater-determinant and beyond

Triggered by the interest to study charge migration in large molecular systems, a simple methodology has recently been proposed based on straightforward density functional theory calculations. This approach describes the time evolution of the initially created hole density in terms of the time evolution of the ionized highest occupied molecular orbital (HOMO). Here we demonstrate that this time-dependent analog of Koopmans' theorem is not valid, and instead of the time evolution of the HOMO, the time evolution of the orbitals that remain occupied in the cation determines the evolution of the initially created hole in the framework of time-dependent single-determinant theories. Numerical examples underline that for a proper description of charge migration processes, an explicit treatment of the electron correlation is indispensable. Moreover, they also demonstrate that the attempts to describe charge migration based on Kohn-Sham density functional theory using conventional exchange-correlation functionals are doomed to fail due to the well-known self-interaction error.