Excited state intramolecular proton transfer mechanism of o-hydroxynaphthyl phenanthroimidazole

By utilizing the density functional theory(DFT) and the time-dependent density functional theory(TDDFT), the excited state intramolecular proton transfer(ESIPT) mechanism of o-hydroxynaphthyl phenanthroimidazole(HNPI) is studied in detail. Upon photo is excited, the intramolecular hydrogen bond is obviously enhanced in the S_1 state, which thus promotes the ESIPT process. Hydrogen bond is shown to be strengthened via comparing the molecular structures and the infrared vibration spectra of the S_0 and S_1 states. Through analyzing the frontier molecular orbitals, we can conclude that the excitation is a type of the intramolecular charge transfer excitation, which also indicates the trend of proton transfer in S_1 state. The vertical excitation based on TDDFT calculation can effectively repeat the absorption and fluorescence spectra of the experiment. However, the fluorescence spectrum of normal structure, which is similar to the spectrum of isomer structure is not detected in the experiment. It can be concluded that the fluorescence measured in the experiment is attributed to both structures. In addition, by analyzing the potential energy curves(PECs) calculated by the B3 LYP functional method, it can be derived that since the molecule to cross the potential barrier in the S_1 state is smaller than in the S_0 state and the reverse proton transfer process in the S_1 state is more difficult than in the S_0 state, the ESIPT occurs in the S_1 state.     

Theoretical investigation on the excited state intramolecular proton transfer in Me_2N substituted flavonoid by the time-dependent density functional theory method

Time-dependent density functional theory(TDDFT) method is used to investigate the details of the excited state intramolecular proton transfer(ESIPT) process and the mechanism for temperature effect on the Enol*/Keto*emission ratio for the Me_2N-substited flavonoid(MNF) compound. The geometric structures of the S_0 and S_1 states are denoted as the Enol, Enol*, and Keto*. In addition, the absorption and fluorescence peaks are also calculated. It is noted that the calculated large Stokes shift is in good agreement with the experimental result. Furthermore, our results confirm that the ESIPT process happens upon photoexcitation, which is distinctly monitored by the formation and disappearance of the characteristic peaks of infrared(IR) spectra involved in the proton transfer and in the potential energy curves. Besides, the calculations of highest occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) reveal that the electronegativity change of proton acceptor due to the intramolecular charge redistribution in the S_1 state induces the ESIPT. Moreover, the thermodynamic calculation for the MNF shows that the Enol*/Keto*emission ratio decreasing with temperature increasing arises from the barrier lowering of ESIPT.     

取代基对2-(2-羟基苯基)苯并噻唑分子内氢键及质子转移的影响:密度泛函理论研究

运用密度泛函(DFT)和含时密度泛函(TD DFT)理论方法研究了在2-(2-羟基苯基)苯并噻唑(HBT)苯环羟基的邻位或对位分别引入羟基和醛基后的衍生物分子内质子转移过程,考察了取代基的电子效应及取代位置对分子内氢键和质子转移反应的影响,模拟计算了各分子的IR振动光谱和电子光谱.研究发现,HBT及其衍生物分子可以形成分子内氢键,且激发态时氢键增强.基态时以醇式构型稳定存在,激发态时酮式结构为优势构象.分子的最大吸收峰和发射峰主要源于电子从前线分子轨道HOMO到LUMO之间的跃迁.基态分子内质子转移需要越过较高的能垒因而难以发生,而激发态时只需越过较低能垒就很容易发生激发态分子内质子转移.取代基的电子效应和取代位置对HBT分子氢键强度、互变异构体的相对稳定性、电子光谱及质子转移反应的能垒均有一定影响.     

A Combined Experimental and DFT-TDDFT Study of the Excited-State Intramolecular Proton Transfer (ESIPT) of 2-(2′-Hydroxyphenyl) Imidazole Derivatives

We report a combined experimental and computational study of the effect of electron donor and acceptor groups on the excited state intramolecular proton transfer of 2-(2′-hydroxyphenyl) imidazole derivatives in solvents of different polarities. The changes in fluorescence properties, electronic transitions and energy levels are analyzed and discussed. The study was complemented using the Density Functional Theory (DFT)-Time Dependent DFT [B3LYP/6-31G(d)] computations. The calculated absorption and emission spectra of the imidazole derivatives are in good agreement with the experiments, thus allowing an assignment of the UV–vis spectra.     

“Charge transfer Complexes of Indolyldiene Aniline derivatives with p-benzoquinone derivatives”

Abstract

Charge transfer (CT) complexes of p-benzoquinone derivatives with Indolyldiene aniline derivatives have been prepared and investigated by Elemental analysis, IR, ¹H-NMR and electronic absorption spectroscopy. The spectral changes revealed that acidic acceptors form complexes with π - π? electronic interaction and proton transfer while non-acidic acceptors yield complexes having π - π transition only. The formation of 1:2 (D:A) complexes is also ascertained. The ionization potential and electron affinity are determined from the electronic absorption spectra for both the donors and acceptors respectivily.     

纳米Gd2O3中两种格位Eu3+的电荷迁移态激发跃迁

观测了粒径分别为15,23,135m的立方相Gd2O3：Eu^3 的选择激发光谱、发射光谱和激发光谱。受强量子限域效应的影响,纳米Gd2O3：Eu^3 的激发光谱的强度表现出对颗粒尺寸的明显依赖性。用Jorgensen公式计算电荷迁移带的位置,与实验测得激发光谱中位置相一致。通过电荷迁移带不同位置的选择激发光谱可以分辨出立方相Gd2O3：Eu^3 中C2和S6格位Eu^3 的发光,从选择激发的发射光谱和激发光谱结果计算出C2和S6格位电荷迁移带的激发光谱,与实验结果相符合。     

Electronic structures and edge effects of Ga_2S_2 nanoribbons

Ab initio density functional theory calculations are carried out to predict the electronic properties and relative stability of gallium sulfide nanoribbons(Ga_2S_2-NRs) with either zigzag- or armchair-terminated edges. It is found that the electronic properties of the nanoribbons are very sensitive to the edge structure. The zigzag nanoribbons(Ga_2S_2-ZNRs)are ferromagnetic(FM) metallic with spin-polarized edge states regardless of the H-passivation, whereas the bare armchair ones(Ga_2S_2-ANRs) are semiconducting with an indirect band gap. This band gap exhibits an oscillation behavior as the width increases and finally converges to a constant value. Similar behavior is also found in H-saturated Ga_2S_2-ANRs,although the band gap converges to a larger value. The relative stabilities of the bare ANRs and ZNRs are investigated by calculating their binding energies. It is found that for a similar width the ANRs are more stable than the ZNRs, and both are more stable than some Ga_2S_2 nanoclusters with stable configurations.     

核苷酸和芳香酮的电子转移和质子转移反应研究

利用时间分辨的激光闪光光解方法在1∶1乙腈/水溶液中得到了4种核苷酸和芳香酮的瞬态吸收光谱,通过瞬态吸收光谱的变化研究了鸟苷酸、腺苷酸、胞苷酸、胸腺苷酸猝灭二苯甲酮、呫吨酮激发三重态的反应。由于实验中生成了抽氢自由基和负离子自由基,以及核苷酸正离子在水中的快速抽氢反应,推断出芳香酮和鸟苷酸、腺苷酸的反应机理是先发生电子转移后发生质子转移。而在芳香酮和胞苷酸、胸腺苷酸的反应中没有观察到相应的抽氢自由基和负离子自由基的瞬态吸收峰,由此推断出它们和胞苷酸、胸腺苷酸没有发生电子转移和质子转移反应。对瞬态吸收峰处的时间衰减曲线进行拟合得到了核苷酸猝灭芳香酮的速率常数,可以看到随着反应自由能变ΔG的增大,反应速率常数逐渐减小。     

非对称核物质中质子和中子的1S0态超流性

利用Brueckner-Hartree-Fock和BCS理论方法，计算了非对称核物质中处于¹S₀态的质子和中子的对关联能隙，着重研究和讨论了能隙的同位旋依赖性和三体核力的影响.结果表明：随核物质的同位旋非对称度增大，中子¹S₀态超流相存在的密度范围逐渐缩小而且对关联能隙峰值稍有升高；质子¹S₀态超流相存在的密度范围迅速扩大而且对关联能隙峰值显著降低.三体核力对非对称核物质中¹S₀态中子超流性及其同位旋依赖性的影响相对较小，但对¹S₀态质子超流性具有重要影响，而且其效应随核子数密度增大而迅速增强.三体核力的主要作用是强烈地抑制了具有高非对称度的核物质中高密度区域的¹S₀态质子超流性，导致质子超流相存在的密度范围显著缩小. 关键词： 同位旋非对称核物质 质子和中子超流性 三体核力 BCS理论     

A Comprehensive Therotical Investigation of Intramolecular Proton Transfer in the Excited States for Some Newly-designed Diphenylethylene Derivatives Bearing 2-(2-Hydroxy-Phenyl)-Benzotriazole Part

This article presents a comprehensive therotical investigation of excited state intramolecular proton transfer (ESIPT) for some newly-designed diphenylethylene derivatives containing 2-(2-hydroxy-phenyl)-benzotriazole moiety with various substituted groups. The calculation shows the structural parameters and Mulliken charges of phototautomers enol (E) and keto (K) of these compounds exhibit no or tiny changes from S₀ to S₁. The calculated results suggest that HOMO and LUMO + 1 of the compounds displays excellent overlapping nature, and thus the absorption and emission could be from the electron transition of HOMO→LUMO + 1. The electron density distribution in the frontier orbital of E and K are influenced remarkably by various substituted groups in S₀ and S₁ states. Electron density distribution deficiency in 2-(2-hydroxy-phenyl)-benzotriazole part is observed in L + 1 for these derivatives. The calculation also suggests the potential energy curves of ESIPT are shown to be a strong relationship with electron donor-acceptor groups. The absorption spectra, normal emission spectra and ESIPT spectra of the derivatives were also calculated.     

瞬态吸收光谱茜素超快动力学研究

激发态质子转移是光物理学、光化学和光生物过程中最基本的化学反应之一。激发态分子内质子转移(excited-state intramolecular proton transfer, ESIPT)通常是指有机分子受到激发,到达激发态后,质子在激发态势能面上从质子供体基团转移到质子受体基团并形成含有分子内氢键多元环的过程, 一般发生在亚皮秒量级。质子转移可应用于有机发光二极管、荧光探针等领域。茜素,即1,2-二羟基蒽醌,可从茜草根部提取,具有与醌类衍生物相似的结构,常用于染料、染色剂和药物等。近年来,发现茜素分子具有质子转移特性,可用来制备新型“绿色”染料敏化电池。利用稳态吸收、稳态荧光和飞秒瞬态吸收光谱技术以及第一性原理理论计算对溶于乙醇溶液的茜素分子的质子转移过程进行了研究和分析。稳态吸收和稳态荧光研究结果表明: 在基态时,茜素分子的正常构型9,10-酮处于稳定状态,容易发生跃迁;在激发态时,茜素分子的互变异构体构型1,10-酮处于稳定状态,容易产生荧光发射。飞秒瞬态吸收光谱测量使用的激光的激发波长为370 nm。测得的瞬态吸收光谱在430 nm附近存在茜素的基态漂白信号。通过使用全局拟合方法对瞬态吸收光谱进行分析研究发现：茜素正常构型9,10-酮的激发态分子内质子转移时间为110.5 fs,茜素互变异构体构型1,10-酮分子内振动弛豫时间为30.7 ps,茜素互变异构体构型1,10-酮荧光寿命为131.7 ps。通过使用单波长动力学拟合的方法对瞬态吸收光谱进行分析发现：发生质子转移的时间尺度与运用全局拟合方法得出的结果基本一致;茜素分子的正常构型9,10-酮分子在110.5 fs的时间尺度内处于快速减少的趋势,而茜素分子的互变异构体构型1,10-酮分子在这一时间尺度内处于快速上升的趋势。当延迟时间增大时,茜素分子的互变异构体构型1,10-酮分子又呈现缓慢衰减的趋势。     

Theoretical study on twisted intramolecular charge transfer of 1-aminoanthraquinone in different solvents

The twisted intramolecular charge transfer and the excited state relaxation of 1-aminoanthraquinone(1-NH_2-AQ)in different solvents are investigated using quantum chemical calculations in this paper.The geometries of the ground state are optimized both in gas and solvents based on the high-level ab initio calculations,the lowest excited singlet state geometry is optimized only in gas for simplicity.An intramolecular charge transfer property is substantiated by the large change of dipole moments between the S_0 and S_1 states.The mechanism of twisted intramolecular charge transfer is proposed by the conformational relaxation on the potential surface of the S_1state.Quantum chemical calculations present that internal conversion and intersystem crossing are important approaches to the ultrafast deactivation of the S_1 state via the twisting of the amino group.The smaller energy difference between the S_0 and S_1 state shows that the internal conversion process is much faster in a polar solvent than in a nonpolar solvent.Energy intersections between the T_2 and S_1 state in cyclohexane and dioxane indicate a faster intersystem crossing process in them than in ethanol.These theoretical results agree well with the previous experimental results.Energy barriers are predicted on the potential surface of the S_1 state,and they have a positive correlation to solvent viscosity,and the timescale of twisted intra-molecular charge transfer in dioxane is predicted to be longer than in cyclohexane and ethanol.     

Excited state intramolecular proton transfer in amino 2-(2′-hydroxyphenyl)benzazole derivatives: Effects of the solvent and the amino group position

The excited-state intramolecular proton transfer (ESIPT) mechanism in six amino 2-(2′-hydroxyphenyl)benzazole derivatives were investigated in different solvents by means of UV-vis absorption and steady-state fluorescence. The amino benzazoles are fluorescent in the blue-orange region under UV radiation. Changes in the absorption, emission and excitation spectra were analyzed and correlated to the position of the amino group and the solvent polarity. The equilibrium between the conformers in solution in the ground state, confirmed by the solvatochromic effect, reflects the dual fluorescence emission presented by these dyes.     

Study of nucleon resonances in a chiral quark model via η productions

In this report we investigate η-meson productions on the proton via electromagnetic and hadron probes in a chiral quark model approach. The observables, such as, differential cross section and beam asym-metry for the two productions are calculated and compared with the experiment. The five known resonances S_(11)(1535), S_(11)(1650), P_(13)(1720), D_(13)(1520), and F_(15)(1680) are found to be dominant in the reaction mech-anisms in both channels. Significant contribution from a new S_(11) resonances are deduced. For the so-called "missing resonances", no evidence is found within the investigated reactions. The partial wave amplitudes for π~-p→ηn are also presented.     

超重核的壳结构

在相对论连续谱Hartree Bogoliubov(RCHB)理论框架下,在质子数Z=100—140和中子数N=Z+30—2Z+32等偶偶核中进行了超重球形双幻核的探索.采用的有效相互作用为NL1,NL3,NLSH,TM1,TW 99,DD ME1,PK1和PK1R.基于对双核子分离能(S2p和S2n)、双核子能隙(δ2p和δ2n)、壳修正能量(Epshell)、对能(Eppair和Enpair)和有效对能隙(Δp和Δn)等物理量和能shell和En级结构的分析,预言了可能的质子幻数和中子幻数,并观察到在超重核区壳的弱化现象. The magic proton and neutron numbers are searched in the superheavy region with proton number Z=100 —140 and neutron number N=(Z+30) — (2Z+32) by the relativistic continuum Hartree-Bogoliubov (RCHB) theory with interactions NL1, NL3, NLSH, TM1, TW99, DD-ME1, PK1, and PK1R. Based on the two-nucleon separation energies S_(2p )and S_(2n) , the two-nucleon gaps δ_(2p) and δ_(2n), the shell correction energies E~p_(shell) and E~n_(shell), the pairing energies E~p_(pair) and E~n_(pair), and...     

As2S8玻璃条形波导的光激励法制备技术研究

为了在As2S8薄膜中制备条形波导,实验研究了As2S8薄膜光致折射率变化和密度变化的现象,采用棱镜耦合、X线衍射和远红外反射光谱等测试技术,确认了As2S8薄膜经紫外光辐照后薄膜密度增高、折射率增大的现象。采用可见光吸收谱测试技术,确认了经紫外光辐照的As2S8薄膜不发生黑化现象。在归纳了实验规律的基础上,提出并采用紫外光激励的方法试制了As2S8条形波导,采用自动调芯端面耦合的方法激励As2S8条形波导的导模,结果显示该波导具有良好的导波特性。     

Structural and aromatic aspects of tautomeric equilibrium in hydroxy aryl Schiff bases

The synthesis and X‐ray measurements of four Schiff bases were carried out at 100 K. The HOMA and HOSE aromaticity indices were estimated on the basis of the experimental data. The aromaticity of the phenyl ring and the chelate chain was analysed. A comparison of the aromaticity of naphthalene and phenyl derivatives of hydroxy aryl Schiff bases is presented. The balance between the aromaticity of adjacent rings of the naphthalene fragment and its effect on proton transfer is defined. Research on the interrelations between aromaticity and the intramolecular proton transfer in hydroxy aryl Schiff bases is shown. Copyright © 2008 John Wiley & Sons, Ltd.     

Magnetic resonance of the weak organic magnet TDAE-C60

The charge transfer compound TDAE-C₆₀ (TDAE — tetrakis-dimethylamino-ethylene) is so far the only known C₆₀ based molecular ferromagnet. The ESR spectra of TDAE-C₆₀ single crystals demonstrate that freshly grown regularly shaped single crystals show at first an AFM (antiferromagnetic)-like behavior which changes upon annealing at room temperature in vacuum to a FM (ferromagnetic) one. It thus seems that annealing induces a change in the relative orientation of the distorted C ₆₀ ^? ions resulting in a change in the sign of the effective magnetic interactions between neighboring C ₆₀ ^? ions. A structural transition in the TDAE methyl protons at 250 K seems to be connected with this process. Here we review the structure, the ESR spectra, the proton NMR spectra and the¹³C NMR spectra of TDAE-C₆₀.     

苯硫酚分子内质子转移取代基效应的理论研究

在B3LYP/6-311+G(d,p)水平上研究了2-(1H-咪唑)苯硫酚(1d)、2-(噁唑)苯硫酚(2d)、2-(噻唑)苯硫酚(3d)及其衍生物的基态质子转移过程,探讨取代基电子效应对质子转移的影响.结果表明:吸电子引入后分子平面电子密度减小,N2-H1间距减小,分子内氢键增强,醇式到酮式质子转移能垒减小;供电子基引入后分子平面电子密度增大,N2-H1间距增大,分子内氢键减弱,质子转移能垒增大.Localized orbital locator(LOL)分析表明:取代基的引入对N1原子成键性质产生影响明显.三者质子转移能垒大小为1d3d2d,取代基引后能垒相对大小不变.