scholarly journals Algorithms for the computer simulation of ultrafast photoinduced intermolecular charge transfer in liquids

2020 ◽  
pp. 27-40
Author(s):  
С.В. Феськов ◽  
С.С. Хохлова
Keyword(s):  
Electron Transfer ◽  
Degrees Of Freedom ◽  
Numerical Solutions ◽  
Kinetic Equations ◽  
Numerical Algorithms ◽  
Electronic States ◽  
Photochemical Reactions ◽  
Solution Of Equations ◽  
Donor Acceptor ◽  
Energy Surfaces

Предложены подходы к численному решению систем уравнений, описывающих кинетику двухстадийной фотохимической реакции в вязком полярном растворителе. Математическая модель построена на основе расширенной интегральной теории встреч и учитывает диффузионную подвижность молекул-реагентов в жидкости, неравновесность среды и внутримолекулярных степеней свободы, удаленный перенос электрона в донорно-акцепторных парах, разделенных растворителем. В рамках метода броуновского моделирования разработаны алгоритмы расчета безреакционных стохастических траекторий частиц на поверхностях свободной энергии, соответствующих различным состояниям реагентов и продуктов, схемы детектирования реакционных событий и генерации электронных прыжков, а также алгоритмы расчета нестационарных потоков частиц между электронными состояниями и вычисления интегральных ядер кинетических уравнений. Представлены результаты тестовых расчетов, демонстрирующие корректность численного решения и воспроизводящие известные особенности реакций электронного переноса в полярных жидкостях. Efficient approaches to the numerical solution of equations describing the kinetics of two-stage photochemical reactions in a viscous polar solvent are proposed. The mathematical model is based on the extended integral encounter theory and takes into account diffusive mobility of reactants in solution, nonequilibrium of solvent and intramolecular degrees of freedom, and remote electron transfer in solvent-separated donor-acceptor pairs. In the framework of the Brownian simulation technique, a number of numerical algorithms for calculating unreactive stochastic trajectories of particles on free energy surfaces corresponding to different electronic states of reactants and products are suggested, some computational schemes for the detection of reaction events and the generation of electronic hops are developed, and algorithms for calculating the time-dependent reaction fluxes between the electronic states and integral kernels of the kinetic equations are implemented. The results of test simulations demonstrating the validity of the numerical solutions and reproducing well-known features of electron transfer reactions in polar solvents are discussed.

scholarly journals Quantum Simulations of Charge Separation at a Model Donor-Acceptor Interface: Role of Delocalization and Local Packing

2018 ◽  
Vol 2018 ◽  
pp. 1-10 ◽  
Author(s):  
Allen Kelley ◽  
Kush Patel ◽  
Eric R. Bittner
Keyword(s):  
Excited States ◽  
Degrees Of Freedom ◽  
Mean Field ◽  
Low Frequency ◽  
Acid Methyl Ester ◽  
Electronic States ◽  
Organic Polymer ◽  
Donor And Acceptor ◽  
Out Of Plane ◽  
Donor Acceptor

Organic Polymer-based photovoltaic systems offer a viable alternative to more standard solid-state devices for light-harvesting applications. In this study, we investigate the electronic dynamics of a model organic photovoltaic (OPV) heterojunction consisting of polyphenylene vinylene (PPV) oligomers and a [6,6]-phenyl C61-butyric acid methyl ester (PCBM) blend. Our approach treats the classical molecular dynamics of the atoms within an Ehrenfest mean-field treatment of the π-π⁎ singly excited states spanning a subset of donor and acceptor molecules near the phase boundary of the blend. Our results indicate that interfacial electronic states are modulated by C=C bond stretching motions and that such motions induce avoided crossings between nearby excited states thereby facilitating transitions from localized excitonic configurations to delocalized charge-separated configurations on an ultrafast time-scale. The lowest few excited states of the model interface rapidly mix allowing low frequency C-C out-of-plane torsions to modulate the potential energy surface such that the system can sample both intermolecular charge-transfer and charge-separated electronic configurations on sub-100 fs time scales. Our simulations support an emerging picture of carrier generation in OPV systems in which interfacial electronic states can rapidly decay into charge-separated and current producing states via coupling to vibronic degrees of freedom.

scholarly journals Non-adiabatic dynamic of atmospheric unimolecular photochemical reactions of 4,4-difluoro-crotonaldehyde using TD-DFT and TSH approaches

2021 ◽  
Author(s):  
Pedro J Castro Pelaez ◽  
Satoshi Maeda ◽  
Keiji Morokuma
Keyword(s):  
Degrees Of Freedom ◽  
Hydrogen Abstraction ◽  
Electronic States ◽  
Photochemical Reactions ◽  
Type I ◽  
Excitation Energies ◽  
Geometrical Structures ◽  
Photochemical Processes ◽  
Norrish Type ◽  
Global Reaction

Photochemical reactions of small molecules occur upon irradiation by ultraviolet or visible light, and they are a very important and controversial chemical process in the Earth’s atmosphere because they impact our quality of life and health. Small-unsaturated carbonyl compounds play an important role in the chemistry of the polluted troposphere. The fluorinated aldehydes are very reactive under the sunlight driving to species that trigger more atmospheric reactions. This paper is focused on a theoretical study of the photochemistry of difluoro-crotonaldehyde using static and dynamic calculations by combination of Global Reaction Route mapping (GRRM) and Trajectory Surface Hopping (TSH) approach. The static analysis of the electronic and geometrical structures at the critical points allowed to rationalize the possible pathways that interconnect the stationary and crossing points in order to get a map of the unimolecular photochemical reactions which take place. The time evolution of the electronic states and the degrees of freedom enabled the identification of the requirements to follow the most probable deactivation pathways. This article reports the unimolecular deactivation pathways after the electronic excitation of the trans and cis isomers. In both cases, the excitation energies were calculated and compared with the analogous in the crotonaldehyde in order to elucidate the effect of fluorine atoms on the electronic structure and stabilities. After the initial excitations to the ππ* excited states, the main deactivation channels follow non-adiabatic pathways via S/S conical intersections. Ultrafast processes leading to the early activation of the S govern the decay of the difluoro-crotonaldehyde. Depending on the nature of the S state before the crossing with the S, the system can follow several reaction pathways. The main photochemical processes observed were the cis-trans isomerization, the Norrish type I reaction (α-cleavage), Norrish type II reaction (γ-hydrogen abstraction) and fluorine photodissociation. The time scale, the molecular deformations and the electronic states implied for the different photochemical processes, as well as how these compete with the photophysical deactivation are discussed.

Excited State Tracking During the Relaxation of Coordination Compounds

2018 ◽  
Author(s):  
Juan Sanz García ◽  
Martial Boggio-Pasqua ◽  
Ilaria Ciofini ◽  
Marco Campetella
Keyword(s):  
Excited State ◽  
Excited States ◽  
Potential Energy Surfaces ◽  
Photochemical Reactions ◽  
Complex Nature ◽  
Electronic Excited States ◽  
Ruthenium Nitrosyl ◽  
State Tracking ◽  
Energy Surfaces ◽  
Electronic Wavefunction

<div>The ability to locate minima on electronic excited states (ESs) potential energy surfaces (PESs) both in the case of bright and dark states is crucial for a full understanding of photochemical reactions. This task has become a standard practice for small- to medium-sized organic chromophores thanks to the constant developments in the field of computational photochemistry. However, this remains a very challenging effort when it comes to the optimization of ESs of transition metal complexes (TMCs), not only due to the presence of several electronic excited states close in energy, but also due to the complex nature of the excited states involved. In this article, we present a simple yet powerful method to follow an excited state of interest during a structural optimization in the case of TMC, based on the use of a compact hole-particle representation of the electronic transition, namely the natural transition orbitals (NTOs). State tracking using NTOs is unambiguously accomplished by computing the mono-electronic wavefunction overlap between consecutive steps of the optimization. Here, we demonstrate that this simple but robust procedure works not only in the case of the cytosine but also in the case of the ES optimization of a ruthenium-nitrosyl complex which is very problematic with standard approaches.</div>

Triatomic molecules

2018 ◽  
Author(s):  
John H. D. Eland ◽  
Raimund Feifel
Keyword(s):  
Degrees Of Freedom ◽  
Normal Modes ◽  
Electronic States ◽  
Triatomic Molecules ◽  
Doubly Charged Ions ◽  
Spectral Bands ◽  
Valence Electrons ◽  
Doubly Charged ◽  
Charged Ions ◽  
Double Ionisation

Double ionisation of the triatomic molecules presented in this chapter shows an added degree of complexity. Besides potentially having many more electrons, they have three vibrational degrees of freedom (three normal modes) instead of the single one in a diatomic molecule. For asymmetric and bent triatomic molecules multiple modes can be excited, so the spectral bands may be congested in all forms of electronic spectra, including double ionisation. Double photoionisation spectra of H2O, H2S, HCN, CO2, N2O, OCS, CS2, BrCN, ICN, HgCl2, NO2, and SO2 are presented with analysis to identify the electronic states of the doubly charged ions. The order of the molecules in this chapter is set first by the number of valence electrons, then by the molecular weight.

scholarly journals An augmented Lagrangian method for solving total variation (TV)-based image registration model

2020 ◽  
Vol 14 ◽  
pp. 174830262097353
Author(s):  
Noppadol Chumchob ◽  
Ke Chen
Keyword(s):  
Image Registration ◽  
Augmented Lagrangian ◽  
Numerical Solutions ◽  
Augmented Lagrangian Method ◽  
Closed Form Solution ◽  
Numerical Algorithms ◽  
Lagrangian Method ◽  
Form Solution ◽  
The Other ◽  
Other Hand

Variational methods for image registration basically involve a regularizer to ensure that the resulting well-posed problem admits a solution. Different choices of regularizers lead to different deformations. On one hand, the conventional regularizers, such as the elastic, diffusion and curvature regularizers, are able to generate globally smooth deformations and generally useful for many applications. On the other hand, these regularizers become poor in some applications where discontinuities or steep gradients in the deformations are required. As is well-known, the total (TV) variation regularizer is more appropriate to preserve discontinuities of the deformations. However, it is difficult in developing an efficient numerical method to ensure that numerical solutions satisfy this requirement because of the non-differentiability and non-linearity of the TV regularizer. In this work we focus on computational challenges arising in approximately solving TV-based image registration model. Motivated by many efficient numerical algorithms in image restoration, we propose to use augmented Lagrangian method (ALM). At each iteration, the computation of our ALM requires to solve two subproblems. On one hand for the first subproblem, it is impossible to obtain exact solution. On the other hand for the second subproblem, it has a closed-form solution. To this end, we propose an efficient nonlinear multigrid (NMG) method to obtain an approximate solution to the first subproblem. Numerical results on real medical images not only confirm that our proposed ALM is more computationally efficient than some existing methods, but also that the proposed ALM delivers the accurate registration results with the desired property of the constructed deformations in a reasonable number of iterations.

Photoelectrochemical properties of supramolecular composites of an anionic zinc chlorin and Li+@C60 on SnO2

2014 ◽  
Vol 18 (10n11) ◽  
pp. 982-990 ◽  
Author(s):  
Kei Ohkubo ◽  
Yuki Kawashima ◽  
Kentaro Mase ◽  
Hayato Sakai ◽  
Taku Hasobe ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Photoinduced Electron Transfer ◽  
Photovoltaic Cells ◽  
Lithium Ion ◽  
Transparent Electrode ◽  
Supramolecular Complex ◽  
Photoelectrochemical Properties ◽  
Triplet Excited State ◽  
Optically Transparent ◽  
Donor Acceptor

An electron donor–acceptor supramolecular complex was formed between an anionic zinc chlorin carboxylate ( ZnCh -) and lithium-ion-encapsulated [60]fullerene ( Li +@ C 60) by an electrostatic interaction in benzonitrile ( PhCN ). Photoinduced electron transfer in the supramolecular complex of ZnCh -/ Li +@ C 60 resulted in the formation of the charge-separated state via electron transfer from the triplet excited state of ZnCh - to Li +@ C 60. We report herein photovoltaic cells using ZnCh -/ Li +@ C 60 nanoclusters, which are assembled on the optically transparent electrode (OTE) of nanostructured SnO 2 (OTE/ SnO 2). The photoelectrochemical behavior of the nanostructured SnO 2 film of supramolecular nanoclusters of ZnCh - and Li +@ C 60 denoted as OTE/ SnO 2/( ZnCh -/ Li +@ C 60)n is significantly higher than the single component films of ZnCh - or Li +@ C 60 clusters, denoted as OTE/ SnO 2/( ZnCh -)n or OTE/ SnO 2/( Li +@ C 60)n.

scholarly journals Hydrodynamic limits of kinetic equations for polyatomic and reactive gases

2017 ◽  
Vol 8 (1) ◽  
pp. 23-42 ◽  
Author(s):  
M. Bisi ◽  
G. Spiga
Keyword(s):  
Degrees Of Freedom ◽  
Continuum Limit ◽  
Fluid Dynamic ◽  
Energy Levels ◽  
Kinetic Equations ◽  
Navier Stokes ◽  
Bgk Model ◽  
Hydrodynamic Limits ◽  
Stress Diffusion ◽  
Reactive Gases

Abstract Starting from a kinetic BGK-model for a rarefied polyatomic gas, based on a molecular structure of discrete internal energy levels, an asymptotic Chapman-Enskog procedure is developed in the asymptotic continuum limit in order to derive consistent fluid-dynamic equations for macroscopic fields at Navier-Stokes level. In this way, the model allows to treat the gas as a mixture of mono-atomic species. Explicit expressions are given not only for dynamical pressure, but also for shear stress, diffusion velocities, and heat flux. The analysis is shown to deal properly also with a mixture of reactive gases, endowed for simplicity with translational degrees of freedom only, in which frame analogous results can be achieved.

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