Scaling for Experimental Inner-Sphere Reorganization Energy of Hydrated Ions via Accurate Potential Function

Reported here are several new calculation methods for the inner-sphere reorganization energy of hydrated metal ions involved in electron transfer processes.It is based on the self-exchange model of reorganization and utilizes the more exact potential functions between central metal ion and the inner-sphere ligands.The parameters involved are determined via the spectroscopic and thermodynamic data.The predictions of the inner-sphere reorganization energies from those models agree well with the photoemission experimental results.

A NEW AB INITIO CALCULATION METHOD OF INNER-SPHERE REORGANIZATION ENERGY

On the basis of the-improved self-exchange model of reorganization phenomenon and accurate potential functions from ab initio calculation at HFSCF 6-31G* and DZP levels a new calculation method was,presented for the inner-sphere reorganization energy, values for diatomic molecular redox couples in gas phase electron transfer process have been calculated. Results agree well with the experimental data, and the effectiveness and importance of this method have been demonstrated for calculation of inner-sphere reorganization energy in gas phase electron transfer process.

The Inner-sphere Reorganization Energy of M-H/M^+-H System in Gaseous Phase

A new ab-initio method of computing reorganization energy (RE) for the electron transfer (ET) reaction between M-H and M+-H system is presented. Values of RE from precise RE definition and the George-Griffith-Marcus (GGM) model were obtained and compared with the RE obtained from the experimental spectroscopic data. Results show that in the gaseous phase, ET reactions by the new method can give better values than classical GGM model.

Judicious training pattern for superior molecular reorganization energy prediction model

Reorganization energy(RE)is closely related to the charge transport properties and is one of the important parameters for screening novel organic semiconductors(OSCs).With the rise of data-driven technology,accurate and efficient machine learning(ML)models for high-throughput screening novel organic molecules play an important role in the boom of material science.Comparing different molecular descriptors and algorithms,we construct a reasonable algorithm framework with molecular graphs to describe the compositional structure,convolutional neural networks to extract material features,and subsequently embedded fully connected neural networks to establish the mapping between features and predicted properties.With our well-designed judicious training pattern about feature-guided stratified random sampling,we have obtained a high-precision and robust reorganization energy prediction model,which can be used as one of the important descriptors for rapid screening potential OSCs.The root-meansquare error(RMSE)and the squared Pearson correlation coefficient(R^(2))of this model are 2.6 me V and0.99,respectively.More importantly,we confirm and emphasize that training pattern plays a crucial role in constructing supreme ML models.We are calling for more attention to designing innovative judicious training patterns in addition to high-quality databases,efficient material feature engineering and algorithm framework construction.

Inner-Sphere Reorganization Eneregy For Metal Ion-Benzene Complex in Electron-Transfer Process

Based on the capture force field potential model and the adiabatic invariant proposed by Bates, adopting improved average dipole orientation (IADO) theory, the force constants between transition metal ions and benzene (bz) and also a series of inner-sphere reoganization energy (REin) were calculated. The reasons for the differences between theoretical predictions and experimental results were discussed.

THE SCALE METHOD OF INNER－SPHERE REORGANIZATION ENERGY OF HYDRATED IONS VIA ION－DIPOLE CAPTUR FORCE FORCE FIELD POTENTIAL

Based on a simple improved model of reorganization phenomenon and ion-dipole fore. field potential, a new formalism of inner-spher reorganization energy is presented Calculation agrees well with experimental spectroscopic scale data and photoemission experimental results.

Solvent Reorganization Energy and Electronic Coupling for Intramolecular Electron Transfer in BiphenyI-Acceptor Anion Radicals

A novel algorithm was designed and implemented to realize the numerical calculation of the solvent reorganization energy for electron transfer reactions, on the basis of nonequilibrium solvation theory and the dielectric polarizable continuum model. Applying the procedure to the well-investigated intramoleeular electron transfer in biphenyl-androstane-naphthyl and biphenyl-androstane-phenanthryl systems, the numerical results of solvent reorganization energy were determined to be around 60 k J/mol, in good agreement with experimental data. Koopman＇s theorem was adopted for the calculation of the electron transfer coupling element, associated with the linear reaction coordinate approximation. The values for this quantity obtained are acceptable when compared with experimental results.

外部技术网络嵌入、知识重组能力与制造企业节能减排

在加快发展方式绿色转型的战略部署下,作为绿色转型的关键实施主体,制造企业不断利用网络嵌入和知识重组以促进其在能源消耗和污染排放工作的平稳、有序推进。本文以中国制造业A股上市公司为研究对象,收集整理企业联合申请发明专利数据,采用社会网络分析软件对外部技术网络嵌入的技术网络地位和网络有效规模进行测算,基于“外部合作-知识重组-节能减排”的逻辑思路分别探索外部技术网络嵌入对制造企业节能减排的直接效应,以及从知识重组视角探讨知识再创造和知识再利用在其中的中介作用。结果表明:技术网络地位和网络有效规模显著有利于降低合作企业的能源消耗和污染排放,知识重组能力在技术网络地位与网络有效规模对节能减排的影响中存在显著中介作用。据此提出相应的管理启示以提高制造企业节能减排成效,为推进“统筹发展与绿色低碳转型,深入实施绿色制造”提供一定的经验证据。

Spectral Shift of π→π^＊ Transition for p-Nitroaniline Based on a New Expression of Nonequilibrium Solvation Energy

According to the nonequilibrium solvation theory studies, a constrained equilibrium principle is introduced and applied to the derivations of the nonequilibrium solvation energy, and a reasonable expression of the spectral shift of the electronic absorption spectra is deduced. Furthermore, the lowest transition of p-nitroaniline （pNA） in water is investigated by time-dependent density functional theory method. In addition, the details of excited state properties of pNA are discussed. Using our novel expression of the spectral shift, the value of -0.99 eV is obtained for π→π^＊ transition in water, which is in good agreement with the available experimental result of -0.98 eV.

DFT and TD-DFT Calculations of Orbital Energies and Photovoltaic Properties of Small Molecule Donor and Acceptor Materials Used in Organic Solar Cells

DFT and TD-DFT calculations of HOMO and LUMO energies and photovoltaic properties are carried out on four selected pentathiophene donor and one IDIC-4F acceptor molecules using B3LYP and PBE0 functionals for the ground state energy calculations and CAM-B3LYP functional for the excited state calculations.The discrepancy between the calculated and experimental energies is reduced by correlating them with a linear fit.The fitted energies of HOMO and LUMO are used to calculate the Voc of an OSC based on these donors and acceptor blend and compared with experimental values.Using the Scharber model the calculated PCE of the donor-acceptor molecules agree with the experiment.It has been found that fluorine substitution can be used to improve charge transport by reducing the electron and hole reorganization energies of the molecules.It is also found that the introduction of fluorine onto the donor pentathiophene unit of the donor molecule results in a change of polarity of the distributed charges in the molecule due to the high electronegativity of the fluorine atom.The quantum chemical potential(μ),chemical hardness(η)and electronegativity(χ),and electrostatic potential maps(EPMs)are also calculated to identify different charge distribution regions in all five molecules.

基于苯并噻吩平面格的张力与重组能的理论研究

有机半导体材料在有机发光二极管(OLED)、有机场效应晶体管(OFET)和有机太阳能电池(OSC)等领域应用广泛,但由于各类结构缺陷和迁移率较低,不利于载流子的传输.本文基于苯并噻吩设计并研究了一系列新型有机电荷传输纳米分子,利用密度泛函理论研究了分子轨道、电离能、电子亲和势、张力能和重组能等分子结构和电子性质;利用约化密度梯度函数和正规模式(NM)分析方法计算了分子内的弱相互作用和每个振动模式对重组能的贡献.结果表明,苯并噻吩格子化(形成四元格)之后,与其单体相比,分子的电子重组能降低了至少0.394 eV,空穴重组能降低了至少0.056 eV,证明格子化是降低重组能的一种有效策略.

Thermodynamics for nonequilibrium solvation and numerical evaluation of solvent reorganization energy

This work presents a thermodynamic method for treating nonequilibrium solvation. By imposing an extra electric field onto the nonequilibrium solvation system, a virtual constrained equilibrium state is prepared. In this way, the free energy difference between the real nonequilibrium state and the con-strained equilibrium one is simply the potential energy of the nonequilibrium polarization in the extra electronic field, according to thermodynamics. Further, new expressions of nonequilibrium solvation energy and solvent reorganization energy have been formulated. Analysis shows that the present formulations will give a value of reorganization energy about one half of the traditional Marcus theory in polar solvents, thus the explanation on why the traditional theory tends to overestimate this quantity has been found out. For the purpose of numerical determination of solvent reorganization energy, we have modified Gamess program on the basis of dielectric polarizable continuum model. Applying the procedure to the well-investigated intramolecular electron transfer in biphenyl-androstane-naphthyl and biphenyl-androstane-phenanthryl systems, the numerical results of solvent reorganization energy have been found to be in good agreement with the experimental fittings.

A Low Reorganization Energy and Two-dimensional Acceptor with Four End Units for Organic Solar Cells with Low E_(loss)

A novel two-dimensional A-D-A acceptor named as CH8 with four electron-withdrawing end units has been successfully designed and synthesized.The enlarged conjugation in two directions renders CH8 exhibit an extremely low electron reorganization energy of 98 meV,which makes CH8 a potential candidate for outstanding organic semiconductor material.When blended with PM6,a considerate power conversion efficiency of 9.37%along with a high open-circuit voltage(V_(oc))0.889 V and low energy loss(E_(loss))below 0.6 eV is achieved.These results indicate that the two-dimensional A-D-A molecule with four electron-withdrawing end units is an effective molecular design strategy to achieve lower voltage loss and also possible high performance for organic photovoltaics if ideal morphology could be achieved.

One approach to calculating the solvent reorganization energy of intramolecular electron transfer

On the basis of the electromagnetic field theory and the spherical cavity approximation, the expressions ofGibbs free energies under equilibrium and non-equilibrium solvation conditions are obtained by solving the electrostatic potential equations with boundary conditions. The surface charges produced by the orientational polarization of equi-librium solvation are taken fixed in the case of non-equilibrium situation, for the slow-response of the orientational polarization to electron transfer of the solvent molecules. Anew expression of solvent reorganization energy has beenobtained and this method is applied to the electron transfer systems, NO+/NO, NO2+/NO2, and NO2+/NO. The solvent reorganization energies have been evaluated.

Internal reorganization energy in heterogeneous intermolecular electron transfer

ELECTRON transfer (ET) reaction is concerned with many important processes in chemistry and biology, and has become an active research field in recent years. According to Marcus’s theory, the ET rate can be expressed as the Fermi’s golden rule:

AM1 and ab initio studies on the internal reorganization energy of self-exchange electron transfer reactions of several quinone derivatives

The semiempirical AMI method, ah initio (HF/3-21G, 6-31G, 6-31G(d), 6-31+G(d)) and DFT (B3LYP/6-31G(d), 6-31+G(d)) methods were used to optimize the geometry of DDQ and its anion radical DDQ-. Nelsen’s model was used to calculate the internal reorganization energy λi of self-exchange electron transfer (ET) reactions. The calculated λi results of DDQ/DDQ-. by AM1 and B3LYP/ 6-31G(d), 6-31+G(d) methods are close to each other and consistent with the reported values; while those from Har-tree-Fock methods are too large because of not consideringthe effect of electron correlation. The structure and ET behavior of MQ0 /MQ0- couple were studied by AM1 and DFT (B3LYP/6-31G(d), 6-31+ G(d, p)) methods, and those of MQ0 /MQn-(n=1-7) were studied by AM1 method for the first time. The results indicate that the values of the heat of formation of MQn increases with the increasing of the length of the isoamylene substituent chains. It also shows that the length of substituent has little effect on the bond lengths,

Internal Reorganization Energy Contributed by Torsional Motion in Electron Transfer Reaction between Biphenyl and Biphenyl Anion Radical

Concerning the theoretical estimation of internal reorganization energy contributed by the tortional motion between biphenyl and biphenyl anion radical, direct calculation of self-exchange electron transfer reaction was investigated. With the introduction of a proper average bond length and angle parameters <bond Bp>, a multiple step relaxation Nelson method was developed to deal with the torsional reorganization energy. Based on the above model, an estimation of pure torsional reorganization energy λ t,p with an approximation of λ t,1 was achieved. The results of 0.140 and 0.125 eV of torsional reorganization energy for a cross-reaction at the levels of 4-31G and HP/DZP, respectively, are in good agreement with the value of 0.13 eV obtained by Miller et al. from the rate measurements. This implies the efficiency and validity of our method to estimate the reorganization energy contributed by pure torsional motion of Bp.

Single-sphere model for solvent reorganization energy and its application to electron transfer

In this work, the authors give detailed deductions and develop the single-sphere model of solvent reorganization energy in electron transfer with point dipole approximation. At the level of DFT/6- 31++G**, the electron transfer between 7,7,8,8-tet-racyanoquinodimethane and its anion has been investigated. Using the novel single-sphere model, the authors evaluate the solvent reorganization energy of this system, and the computational result proves rational in comparison with the experimental estimations.

蒽类衍生物的电荷传输性质

以具有较高迁移率的对称取代类蒽的衍生物{2,6-二[2-(4-戊基苯基)乙烯基]蒽,DPPVAnt;2,6-二-噻吩蒽,DTAnt;2,6-二[2-己基噻吩]蒽,DHTAnt}为研究对象,采用密度泛函理论的B3LYP方法,在6-31G(d)的基组水平上研究了三种蒽类衍生物的分子结构、电子结构、重组能和电荷传输积分,采用Einstein关系式计算了室温下的载流子迁移率,并与蒽的相关计算结果进行了比较.DPPVAnt是较好的空穴传输材料,其空穴迁移率为0.49cm2·V-1·s-1;DHTAnt有利于电子传输,其电子迁移率为0.12cm2·V-1·s-1;而DTAnt是一种较好的双极性材料,其空穴迁移率和电子迁移率分别为0.069和0.060cm2·V-1·s-1.计算得到的迁移率与实验结果处于同一数量级.三种蒽类衍生物的电子重组能与蒽的相近,而空穴重组能均大于蒽的空穴重组能,大小顺序为蒽<DPPVAnt<DTAnt<DHTAnt.这与计算的迁移率结果不一致,说明分子的堆积结构决定材料的电荷传输性质.

萤火虫氧化荧光素及其衍生物的电子结构和光物理性质

通过密度泛函理论(DFT)的MPW3PBE泛函,对萤火虫生物发光底物氧化荧光素及其衍生物进行了结构全优化.计算了其电离能、电子亲和势、空穴抽取能、电子抽取能、空穴和电子重组能,并评估了其空穴和电子传输能力.采用含时密度泛函理论(TD-DFT)//MPW3PBE/6-31+G(d)方法计算了吸收光谱,优化了最低单重态S1,研究了其荧光光谱,进而考察了具有较高发光效率的氧化荧光素作为有机发光二极管(OLED)材料的可能性.计算结果表明,氧化荧光素及其衍生物可以同时作为电子传输层和发光层材料.