Charge Transfer Properties of Organic Semiconductor Molecules of Perylene Derivatives

The charge transfer rates of perylene and its four derivatives were studied at the level of B3LYP/6-31G＊＊ by density functional theory. The results showed that the perylene and its four derivatives belonged to the semiconductor molecules, which released energy when electron was injected. Therefore, they were suitable to be used as the electron injection material. The introduction of OH group can improve the electron transfer rate significantly. The formations of intramolecular hydrogen bonds were unfavorable to the hole transfer, but conducive to the electron transfer. The perylene derivatives, 2,5-3,4,5-（trifluorophenyl）ethynyl-8,11-3,4,5-trihydroxyphenyl ethynyl, designed in this article had the hole transfer rate of 1.57 cm2/V·s·1. Therefore, this kind of material will be potential hole transfer material with high transfer efficiency.

Mechanistic Investigation on Rhodium(III)-Catalyzed Cycloaddition of 2-Vinylphenol Derivatives with Ethyne or Carbon Monoxide by DFT Study

Rhodium-catalyzed cycloaddition reaction was calculated by density functional theory M06-2X method to directly synthesize benzoxepine and coumarin derivatives.In this work,we conducted a computational study of two competitive mechanisms in which the carbon atom of acetylene or carbon monoxide attacked and inserted from two different directions of the six-membered ring reactant to clarify the principle characteristics of this transformation.The calculation results reveal that:(i)the insertion process of alkyne or carbon monoxide is the key step of the reaction;(ii)for the(5+2)cycloaddition reaction of acetylene,higher energy is required to break the Rh−O bond of the reactant,and the reaction tends to complete the insertion from the side of the Rh−C bond;(iii)for the(5+1)cycloaddition of carbon monoxide,both reaction paths have lower activation free energy,and the two will generate a competition mechanism.

Correlation between Chromatograph Capacity Factors and Structural Parameters of Indole Derivatives

Sixteen indole derivatives have been computed at B3LYP/6-31 IG^＊＊ level using density functional theory （DFF）. Based on linear solvation energy theory, the structural parameters were employed to present correlation between the parameters of chromatograph capacity factor （CCF） and molecular structural parameters. As a result, the correlation equation of the reversed phased high performance liquid chromatograph capacity factor to the intercept lgk＇w and slope S of CCF were obtained, from which the correlation coefficients of lgk＇w to the structural parameters are r^2 = 0.9596 and q^2 = 0.9262. While the correlation coefficients of the parameter S r^2 q^2 with structures are = 0.9750 and = 0.9252. Moreover, the effect of water as solvent on the present two models was also considered using SCRF method, and the result shows that the predicting capacity of correlation equation of lgkw＇ increases, while that of the model for S decreases slightly. Both two correlation equations achieved in this work are more advantageous than those using theoretical descriptors from molecular connectivity indices.

Functionals and Functional Derivatives of Wave Functions and Densities

It is shown that the process of conventional functional differentiation does not apply to functionals whose domain (and possibly range) is subject to the condition of integral normalization, as is the case with respect to a domain defined by wave functions or densities, in which there exists no neighborhood about a given element in the domain defined by arbitrary variations that also lie in the domain. This is remedied through the generalization of the domain of a functional to include distributions in the form of , where ?is the Dirac delta function and is a real number. This allows the determination of the rate of change of a functional with respect to changes of the independent variable determined at each point of the domain, with no reference needed to the values of the functional at different functions in its domain. One feature of the formalism is the determination of rates of change of general expectation values (that may not necessarily be functionals of the density) with respect to the wave functions or the densities determined by the wave functions forming the expectation value. It is also shown that ignoring the conditions of conventional functional differentiation can lead to false proofs, illustrated through a flaw in the proof that all densities defined on a lattice are -representable. In a companion paper, the mathematical integrity of a number of long-standing concepts in density functional theory are studied in terms of the formalism developed here.

The Pursuit of Fallacy in Density Functional Theory: The Quest for Exchange and Correlation, the Rigorous Treatment of Exchange in the Kohn-Sham Formalism and the Continuing Search for Correlation

As pointed out in the paper preceding this one, in the case of functionals whose independent variable must obey conditions of integral normalization, conventional functional differentiation, defined in terms of an arbitrary test function, is generally inapplicable and functional derivatives with respect to the density must be evaluated through the alternative and widely used limiting procedure based on the Dirac delta function. This leads to the determination of the rate of change of the dependent variable with respect to its independent variable at each isolated pair, , that may not be part of a functional (a set of ordered pairs). This extends the concept of functional derivative to expectation values of operators with respect to wave functions leading to a density even if the wave functions (and expectation values) do not form functionals. This new formulation of functional differentiation forms the basis for the study of the mathematical integrity of a number of concepts in density functional theory (DFT) such as the existence of a universal functional of the density, of orbital-free density functional theory, the derivative discontinuity of the exchange and correlation functional and the extension of DFT to open systems characterized by densities with fractional normalization. It is shown that no universal functional exists but, rather, a universal process based only on the density and independent of the possible existence of a potential, leads to unique functionals of the density determined through the minimization procedure of the constrained search. The mathematical integrity of two methodologies proposed for the treatment of the Coulomb interaction, the self-interaction free method and the optimized effective potential method is examined and the methodologies are compared in terms of numerical calculations. As emerges from this analysis, the optimized effective potential method is found to be numerically approximate but formally invalid, contrary to the rigorously exact results of the self-interaction-free method.

Rational molecular engineering towards efficient heterojunction solar cells based on organic molecular acceptors

The selection of photoactive layer materials for organic solar cells(OSCs) is essential for the photoelectric conversion process.It is well known that chlorophyll is an abundant pigment in nature and is extremely valuable for photosynthesis.However,there is little research on how to improve the efficiency of chlorophyll-based OSCs by matching chlorophyll derivatives with excellent non-fullerene acceptors to form heterojunctions.Therefore in this study we utilize a chlorophyll derivative,Ce_(6)Me_(3),as a donor material and investigate the performance of its heterojunction with acceptor materials.Through density functional theory,the photoelectric performances of acceptors,i ncluding the fullerene derivative PC_(71)BM and the terminal halogenated non-fullerene DTBCIC series,are compared in detail.It is found that DTBCIC-C1 has better planarity,light absorption,electron affinity,charge reorganization energy and charge mobility than others.Ce_(6)Me_(3) has good energy level matching and absorption spectral complementarity with the investigated acceptor molecules and also shows good electron donor properties.Furthermore,the designed Ce_(6)Me_(3)/DTBCIC interfaces have improved charge separation and reorganization rates(K_(CS)/K_(CR)) compared with the Ce_(6)Me_(3)/PC_(71)BM interface.This research provides a theoretical basis for the design of photoactive layer materials for chlorophyll-based OSCs.

噻吩酰亚胺衍生物二阶非线性光学性质的DFT研究

采用密度泛函理论(DFT)CAM-B3LYP方法,计算研究了12个设计的噻吩酰亚胺衍生物的电子光谱和二阶非线性光学性质.结果表明,此类化合物有较大的第一超极化率β_(tot)值和β_(vec)值,且β_(tot)值和β_(vec)值随引入氰基数目的增加而显著增大.给/吸电子基团引起的电荷转移变化对体系β_(tot)值和β_(vec)值的影响大于分子六元杂环中N杂原子位置变化对其影响.

Theoretical Investigation on QSAR of(2-Methyl-3-biphenylyl)methanol Analogs as PD-L1 Inhibitor

Cancer is one of the most serious issues in human life.Blocking programmed cell death protein 1 and programmed death ligand-1(PD-L1)pathway is one of the great innovations in the last few years,a few numbers of inhibitors can be able to block it.(2-Methyl-3-biphenylyl)methanol derivative is one of them.Here,the quantitative structure-activity relationship(QSAR)established twenty(2-methyl-3-biphenylyl)methanol derivatives as the programmed death ligand-1 inhibitors.Density functional theory at the B3LPY/6-31+G(d,p)level was employed to study the chemical structure and properties of the chosen compounds.Highest occupied molecular orbital energy EHOMO,lowest unoccupied molecular orbital energy ELUMO,total energy ET,dipole moment DM,absolute hardnessη,absolute electronegativityχ,softness S,electrophilicityω,energy gap?E,etc.,were observed and determined.Principal component analysis(PCA),multiple linear regression(MLR)and multiple nonlinear regression(MNLR)analysis were carried out to establish the QSAR.The proposed quantitative models and interpreted outcomes of the compounds were based on statistical analysis.Statistical results of MLR and MNLR exhibited the coefficient R^2 was 0.661 and 0.758,respectively.Leave-one-out cross-validation,r_m^2 metric,r_m^2 test,and"Golbraikh&Tropsha’s criteria"analyses were applied for the validation of MLR and MNLR,which indicate two models are statistically significant and well stable with data variation in the external validation towards PD-L1.The obtained results showed that the MNLR model predicts the bioactivity more accurately than MLR,and it may be helpful and supporting for evaluation of the biological activity of PD-L1 inhibitors.

Toxicity (-lgEC_(50)) Measurement of the Fluorobenzene Derivants against Vibrio Qinghaiensis (Q67) and Their 2D,3D-QSAR Study

Toxicities （-lgEC50） of 16 fluorobenzene derivants against vibrio qinghaiensis （Q67） were measured systematically,and their quantum chemistry parameters were calculated at the B3LYP/6-311G＊＊ level. Based on the experimental toxicity data and quantum chemistry parameters,2D-QSAR model was proposed,which was validated by variance inflation factors （VIF）,t-value and cross-validation method. At the mean time,comparative molecular force field （CoMFA） based on molecular simulation was used to investigate the toxicity of fluorobenzene derivants. Furthermore,the intoxicating mechanism of fluorobenzene derivants was discussed. To our interest,2D-QSAR and CoMFA models exhibit good prediction ability,with which the toxicity of similar compounds can be predicted. Finally,toxicities （-lgEC50） of 12 fluorobenzene derivants against vibrio qinghaiensis （Q67） were predicted with these models.

Determination of lgK_(ow) and QSPR Study on Some Fluorobenzene Derivatives

In this paper, n-octanol/water partition coefficients （1gKow） of 15 fluorobenzene derivatives at 25 ℃ were determined with shake-flask method. Molecular structures of 19 fluorobenzene derivatives were fully optimized with B3LYP method of density functional theory （DFT） on the 6-311G^＊＊ basis set. The obtained structural parameters and thermodynamic parameters were taken as theoretical descriptors with SPSS 12.0 for windows program so as to obtain the predicted correlation model of 1gKow. Its correlation coefficient R^2 is 0.966, and the model was verified with variance inflation factor （VIF） and t vaine so that the cross-validation coefficient （q^2） was obtained as 0.931. In addition, the four homogeneous compounds were predicted.

TD-DFT Study on Pyrazoline Derivatives

The molecular structures of ground state and first single excited state for pyrazoline derivatives are optimized with DFT B3LYP method and ab initio “configuration interaction with single excitations”（CIS） method, respectively. The frontier molecular orbital characteristics have been analyzed systematically, and the electronic transition mechanism has been discussed. Electronic spectra are calculated by using TD-DFT method. These results are consistent with those from the experiment.

Quantum Chemical Studies on the Corrosion Inhibition of Mild Steel by Piperidin-4-One Derivatives in 1 M H₃PO₄

The corrosion inhibition properties of 2,6-diphenylpiperidin-4-one (DPP) (1A) and 2,6-diphenyldihydro-2H-thiopyran-4(3H)-one (DPDT) (1B) for mild steel in 1 M phosphoric acid were studied using weight loss, potentiodynamic polarization and electrochemical impedance spectroscopic techniques. The effect of temperature on the corrosion behavior of mild steel has been examined in the temperature range 303 - 328 K. The inhibition efficiency increases with increasing inhibitor concentration but decreases with increasing temperature. Potentiodynamic polarization studies indicated the mixed nature of inhibitors. The adsorption of the inhibitors on mild steel surface obeyed the Langmuir adsorption isotherms. The density functional theory (DFT) at the B3LYP/6- 31G (d) basis set level was performed on 1A and 1B to investigate the correlation between molecular structure and the corresponding inhibition efficiency (%). The quantum chemical parameters such as EHOMO, ELUMO, the energy gap (E), hardness (η), softness (S), dipole moment (μ), electron affinity (A), ionization potential (I), the absolute electronegativity (χ), the fraction of electron transferred (N), electrophilicity index (ω), the back-donation (EBack-donation) and Mulliken population analysis have been calculated.

Low-Frequency Vibrations of Indole Derivatives by Terahertz Time-Domain Spectroscopy

Several indole derivatives with different ＇3-＇ substituents have been investigated by terahertz （THz） time-domain spectroscopy. The low-frequency absorption spectra and refractive indices were obtained in the range of 0.2 THz to 2.5 THz （7 cm-1 to 83 cm-1）. These derivatives with different substituents present distinct features, which suggests that THz spectroscopy is sensitive to different structures and components of these chemicals. The density functional theory was employed to calculate the low-frequency vibrational properties of indole-3-carboxylic acid and indole-3-propionic acid based on their crystal structures, and the intermolecular interactions were involved. Meanwhile, the temperature dependence of the spectra agreed with the calculated results. The quantitative analysis of a ternary mixture was studied by taking the THz fingerprints into account, and the results demonstrate THz spectroscopy has great potential for the practical applications in biochemistry and pharmaceutics.

Theoretical Study on the Electronic Structures and Spectral Properties of 1,8-Naphthalimide Derivatives

The molecular geometries, frontier molecular orbital properties, and absorption and emission properties of three 4-phenoxy-1,8-naphthalimide derivatives, namely 4-phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（1）,4-（2-tert-butylphenoxy）-N-（2-hydroxyethyl）-1,8-naphthalimide（2）, and 4-[2,4-di（tert-butyl）]phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（3）, are investigated by density functional theory（DFT） and time-dependent density functional theory（TD-DFT） calculations in conjunction with polarizable continuum models（PCMs）. Four functionals and ten basis sets are employed for 1 to calculate the electron transition energies, which were compared with the experimental observations. Our results reveal that the B3LYP/6-311＋G（d,p） method is the best choice to reproduce the experimental spectra. Moreover, the effects of substituents on the molecular geometries, electronic structures, absorption and emission spectra are also studied at the B3LYP/6-311＋G（d,p） level. We find that the gap between the highest occupied molecular orbital（HOMO） and the lowest unoccupied molecular orbital（LUMO） decreases with increasing the number of tert-butyl substituents onto the phenoxy groups, suggesting red-shift of the absorption and emission bands. This is related to the increase of conjugation from 1 to 2 and 3. Our calculations are in good agreement with the experimental results.

Quantum Chemistry Study on Benzimidazoledithi Derivatives' Selective Pre-enrichment of Cadmium Cation

This work reports the mechanism of benzimidazoledithi(BDT) derivatives’ selective pre-enrichment of Cd2+under the stimulation of glutathione(GSH). The geometric and electronic properties of five BDT-M2+complexes(M = Cd, Cu, Hg, Pb, Co) have been investigated using density functional theory(DFT) at the B3 LYP/6-311 G(d,p) level with the GAUSSIAN 09 package program. The results show that BDT ligand exhibits alternative behaviors to different metal ions with the binding affinity in the order of Cu2+> Cd2+> Pb2+> Hg2+> Co2+. After adding the BDT-M2+complex into the GSH solution, the new S–S bonds can be formed, resulting with benzimidazole-metal ions(MBI-M2+) falling off into the GSH solution. Furthermore, the weak interaction between the new glutathione derivative(GSHD) and MBI-M2+were found. However, the strong chelation was detected between GSHD and MBI-M2+(M = Cu, Pb, Hg, Co) to hinder the adsorbed Cu2+, Pb2+and Hg2+, Co2+completely falling into the GSH solution, which suggests porous silicon composite modified by BDT has a certain selective pre-enrichment of Cd2+ion.

UV-Vis Spectrum and the Third-order Nonlinear Optical Properties of the Chiral Camphorderived β-diketonate Platinum Complexes

UV-Vis spectrum and the third-order nonlinear optical properties of the chiral camphor-derived β-diketonate have been studied at the B3LYP/6-31G＊ level. The results showed that the introduction of electron-drawing group -CF3 and -C3F7 on β-diketonate made the strongest absorption peak red-shift and the lowest energy absorption blue-shied. Introduction of -OC2H5 on the benzene or pyridine ring made the lowest energy absorption blue-shift. When the -C2H3 was introduced on the benzene or pyridine ring, the lowest energy absorption was red-shifted. Introduction of electron-donating group on β-diketonate can enlarge their nonlinear optical properties. On the contrary, the introduction of electron-drawing group dropped it down.

Infrared Photodissociation Spectroscopic and Theoretical Study of the HC2nO+（n=3-6） Cations

The carbon chain cations, HC2nO+(n=3-6) are produced via a pulsed laser vaporization supersonic expansion ion source in the gas phase. Their infrared spectra are measured via mass-selected infrared photodissociation spectroscopy of the CO “tagged”[HC2nO·CO]+ cation complexes in 1600-3500 cm-1 frequency range. The geometric and electronic structures of the [HC2nO·CO]+ complexes and the core HC2nO+(n=3-6) cations are determined with the aid of density functional theory calculations. These HC2nO+(n=3-6) ions are identified to be linear carbon chain derivatives terminally capped by hydrogen and oxygen. The triplet ground states are 10-15 kcal/mol lower in energy than the singlet states, indicating cumulene-like carbon chain structures.

Computational Investigation of the Substituent Effect on the Intramolecular Proton Transfer Reaction of 3-Hydroxytropolone

The effects of substituent type and position on the proton transfer reaction of 3-hydroxytropolone(3-OHTRN) have been investigated theoretically by using density functional theory at the level of B3LYP/ 6-31+G** method. The influence of solvent on the proton transfer reactions of substituted 3-OHTRN has been examined using the self-consistent isodensity polarized continuum model(SCI-PCM) in water. As a result, while the proton transfer reaction is kinetically the easiest by substitution on position 3 of-NH2 group in the gas phase, it is kinetically the easiest by substitution on position 5 of the same group in water. In addition, these reactions are either kinetically or thermodynamically easier in the gas phase than that in water, except the reaction of structure with-NH2 group at position 6.

Cu(Ⅱ)结合对3种黄酮醇分子结构与抗氧化活性影响的理论分析

为揭示黄酮醇与Cu(Ⅱ)之间的相互作用机制,进而提升黄酮醇-Cu(Ⅱ)配位化合物的抗氧化活性,采用密度泛函理论B3LYP方法,分析了羟基去质子化及结合Cu(Ⅱ)对水溶液中3种林源膳食黄酮醇山奈酚、槲皮素、杨梅素分子结构与抗氧化活性的影响。结果表明:羟基去质子化后,黄酮醇分子内其他O—H键键长减小、苯环结构二面角发生改变、分子偶极矩增加、最高占有分子轨道(HOMO)与最低未占有分子轨道(LUMO)能级差(ΔE)减小、分子内其他羟基氢原子正电荷数减小;结合Cu(Ⅱ)后,黄酮醇分子内其他O—H键键长增加、二面角与偶极矩改变、ΔE减小、氢原子正电荷数增大。研究还发现:去质子化后的黄酮醇主要通过改变分子结构和减小ΔE提升离子活性,于去质子化位点形成较高负电势,从而通过静电相互作用与Cu(Ⅱ)发生配位;结合Cu(Ⅱ)后的黄酮醇主要通过增加键长、改变分子结构、增加氢原子正电荷数促进与自由基结合,减小ΔE提升分子活性,增强其抗氧化能力。

近红外荧光探针增强共轭DDAO衍生物荧光团的理论设计及结构、电子和光谱性质研究

为提升1,3-二氯-7-羟基-9,9-二甲基-2(9H)-吖啶酮(1,3-dichloro-7-hydroxy-9,9-dimethly-2(9H)-acridinone,DDAO)的荧光成像效果,从理论上设计了5种增强共轭DDAO衍生物,引入双氰基异佛尔酮,增强受体能力及DDAO衍生物的共轭程度。采用密度泛函理论(density functional theory,DFT)探讨了强共轭DDAO衍生物的荧光响应机制和特性,并分析DDAO及其衍生物优化后的结构变化、激发和发射过程中的电子转移及跃迁性质等。结果表明,DDAO衍生物的供体-π-受体(donor-π-acceptor,D-π-A)结构存在增强的分子内电荷转移(intramolecular charge transfer,ICT)效应,导致荧光发射波长最大移至1295.01 nm。该研究证实了引入取代基能产生强共轭,使激发前后产生较大的斯托克斯(Stokes)位移。