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1.
获取了1-甲基胸腺嘧啶(MT)涵盖紫外光谱中A带和B带吸收的共5 个激发波长的共振拉曼光谱, 并结合密度泛函理论方法研究了MT的电子激发和Franck-Condon 区域结构动力学. 在TD-B3LYP/6-311++G(d,p)计算水平下, A带和B带吸收被分别指认为πH→πL*H-2→πL+2*和πH→πL+2H-2→πL*跃迁. 甲基参与嘧啶环的共轭使MT的A带最大吸收波长λmax相对于胸腺嘧啶(T)发生明显红移, 并对Franck-Condon区域的动态结构产生一定影响. A带和B带共振拉曼光谱分别被指认为14 个振动模式和11 个振动模式的基频、泛频和组合频. C5=C6伸缩+C6H12面内弯曲振动v9, 环变形振动v16和N3C2N1反对称伸缩+C4C5C10反对称伸缩振动v18占据了A带共振拉曼光谱强度的绝大部分. 这表明1πHπL*激发态结构动力学主要沿这些反应坐标展开. 考察了溶剂对共振拉曼光谱的影响, 结果表明, C4=O9伸缩+N3H11面内弯曲振动v8的活性与溶剂性质有关, 其激发态位移量随溶剂性质的变化规律与胸腺嘧啶一致.  相似文献   

2.
采用广义梯度近似的密度泛函理论并结合平板模型的方法, 优化了糠醛分子在Pt(111)面的吸附模型,并探究了糠醛脱碳反应形成呋喃的机理. 结果表明: 吸附后糠醛分子环上的C―H(O)键及支链―CHO相对于金属表面倾斜上翘, 分子平面被扭曲, 易于呋喃的形成; 同时, 糠醛分子向Pt表面转移电子0.765e, 环中的大π键与Pt(111)表面的d轨道发生较强的相互作用, 使得糠醛的芳香性被破坏, 环上的碳原子呈现准sp3杂化. 此外, 对糠醛脱碳反应中的各反应步骤进行过渡态搜索, 通过比较各步骤的活化能, 得出糠醛更易先失去支链上的H形成酰基中间体(C4H3O)CO, 中间体继续脱碳加氢形成产物呋喃. 该过程的控速步骤为(C4H3O)CO*+*→C4H3O*+CO* (*为吸附位),活化能为127.65 kJ·mol-1.  相似文献   

3.
马艳平  包鹏  虞忠衡 《化学学报》2006,64(13):1304-1308
为了探索DFT方法中氮苄叉基苯胺分子的扭曲驱动力, 通过把非平面氮苄叉基苯胺(NBA)分子的DFT能量分成π和σ的方法, 分析了垂直离域能ΔEV(θ)及σ-π轨道作用能ΔEσπ(θ)的失稳定性, 并讨论了在扭曲过程中它们所起的作用. 在B3LYP/6-31G*, 6-311G*, 6-31G(2d), 6-311G(2d)水平下的计算结果显示: 与经典观点不同, π电子的离域是失稳定的, 且平面时失稳定性最强, 是分子扭曲的动力; 但σ-π轨道作用也是失稳定的, 随着扭角的增大其失稳定性增强, 是分子扭曲的阻力. NBA分子的大扭角构象, 是包含π-π, σ-π轨道作用在内的各种电子相互作用共同作用的结果.  相似文献   

4.
采用半经典动力学方法模拟了π堆积的胸腺嘧啶体系最低激发态的光物理失活过程.设置激光脉冲仅作用于一个胸腺嘧啶分子T,另一胸腺嘧啶分子T’保持基态.模拟发现由于T与T’之间存在π堆积相互作用,导致电荷转移,形成T带负电荷、T’带正电符的激基复合物.由于相邻分子的空间效应阻碍了激发的T分子到达圆锥相交所必需的强烈扭曲,激基复合物的寿命比单体增长.当分子间距离缩短至0.3 nm后,T分子C5—C6键扭曲程度最大,此时发生电荷重组,两个胸腺嘧啶分子均恢复电中性.电荷重组诱导T’分子发生畸变,并在C5’—C6’扭曲最大时避免相交,体系衰减至基态,T和T’分子均恢复平面构型.  相似文献   

5.
利用纳秒级激光光解瞬态吸收光谱研究了联苯甲酰(BZ)在离子液体1-丁基-3-甲基咪唑四氟硼酸盐([bmim][BF4])与乙腈(MeCN)混合体系中的光化学反应行为. 考察了探针分子BZ存在下[bmim][BF4]/MeCN比例对体系中化学反应动力学的影响. 实验发现: 在N2饱和条件下, BZ溶液经激光辐照后产生的激发三线态3BZ*遵循一级反应动力学规律衰减. 离子液体(IL)相对比例增加对3BZ*瞬态吸收峰的位置和强度没有产生明显影响. 但离子液体体积分数VIL的变化对[bmim][BF4]/MeCN混合溶剂中光诱导电子转移的影响却非常显著, 总体上电子转移产生的自由基的表观生成速率常数kgr随[bmim][BF4]的VIL增大而减小. 在[bmim]BF4]比例足够大的情况下, 3BZ*与三乙胺或四甲基对苯二胺之间的电子转移被抑制.  相似文献   

6.
采用密度泛函理论对原儿茶酚3,4-双加氧酶(3,4-PCD)活化O2分子的反应机理进行了探讨. 初始复合物, 六重态61的超快形成主要归因于电子交换诱导系间穿越(EISC), Fe dz:O2 π*(z)是主要的交换通道, 在Fe―O键长为0.2487 nm处, 交换重叠积分Sij=ádz α|π*(z) β>=0.3758. 从六重态61 形成四重态中间体41, 有两种效应共存, 即电子交换耦合作用和自旋轨道耦合(SOC)作用, 且相互竞争. 计算结果表明, 自旋轨道耦合(SOC)作用起主导因素(SOC=353.16 cm-1). 至于O―O键的解离主要取决于儿茶酚(PCA)最高占据分子轨道(HOMO)的电子转移, 非血红素酶的铁中心仅承担PCA向O2电子转移的缓冲作用.22  相似文献   

7.
赵岷  张元  王璐 《物理化学学报》2011,27(3):584-588
采用密度泛函理论B3LYP/6-31G*方法, 对一系列含咔唑生色团的有机芳香杂环分子进行结构优化, 并采用有限场(FF)和含时密度泛函理论(TD-DFT)方法在6-311G**水平上探讨了体系的二阶非线性光学(NLO)性质和电子光谱. 结果表明, 咔唑取代基推或拉电子能力的改变和引入芳香杂环对研究分子的极化率α和二阶NLO系数β值都有较大影响. 当取代基分别连有拉电子硝基和推电子羟基, 以及引入呋喃杂环都可以使体系分子的β值随分子的最大吸收波长λmax的增大而减小(蓝移). 该系列化合物兼具有很大的二阶非线性响应与良好的透光范围, 避免了“非线性-透光性”矛盾, 可能在非线性材料领域中有很大的潜在应用价值.  相似文献   

8.
魏婧  程文旦 《物理化学学报》2013,29(10):2215-2220
采用密度泛函理论(DFT)-B3LYP方法在6-31G*基组水平上,对芳香性氨基酸分子体系(Phe, [Phe―H]-,PheH*, Tyr, [Tyr―H]-, TyrH+, Trp, [Trp―H]-和TrpH+)进行结构优化. 在优化所得构型的基础上, 利用含时密度泛函理论(TDDFT)-B3LYP在6-31G*基组上计算了它们的激发态性质,并结合态求和方法研究了它们在二次谐波过程中的二阶极化率值. 同时讨论了二次谐波非线性光学响应的起源及其产生变化的原因. 计算结果表明,相对于中性的氨基酸分子, 去质子化和质子化后的氨基酸分子的二阶极化率值都有明显的增加, 且符合规律Phe < PheH+ < [Phe―H]-和Tyr < TyrH+ < [Tyr―H]-. 通过对它们电极化起源的分析, 我们得到对于中性氨基酸分子, 侧链芳香环上的π→π*跃迁对二阶极化率起主要贡献; 对去质子化和质子化后的氨基酸分子, 吲哚环上的π→π*电荷跃迁和α碳原子相连的氨基和羧基基团内电荷跃迁对二阶极化率起到同样重要的贡献.  相似文献   

9.
采用密度泛函理论(DFT)方法, 在B3LYP/6-31G* 水平上对乙烯基噻吩共轭螺噁嗪化合物 SO-SO3 的几何构型、电子结构、前线分子轨道等进行了理论研究, 计算结果表明: SO-SO3的开环过程会使得开环体的左右两个部分键长均等化, 导致共轭体系变大, 能隙明显减小; 乙烯基噻吩基团共轭接入螺噁嗪母体后, 导致体系的共轭作用变大, 在激发态下电子流动增强, 形成由乙烯基噻吩向萘并噁嗪的有效电荷转移与能量转移; 结合前线分子轨道成分分析乙烯基噻吩单元在最高占据分子轨道(HOMO)和最低未占据分子轨道(LUMO)中的轨道贡献率明显增加. 含时密度泛函理论(TD-DFT)计算的电子吸收光谱结果显示: 当接入的乙烯基噻吩单元达到2-3个时, 影响SO2和SO3开环的最低能量激发态变为第一激发单重态S1, 并且均源自电子从HOMO至LUMO的跃迁且为π-π*跃迁; 其最大吸收波长λmax 达到466-540 nm, 且红移十分明显, 其对应开环体O-SO2与O-SO3的λmax 达到605和647 nm.  相似文献   

10.
采用密度泛函理论B3LYP方法, 对两类金(I)配合物AuX (X=F, Cl, Br, I)和AuPR3+(R=F, Cl, Br, I, H, Me,Ph)催化C2H4加氢反应的机理进行了理论研究. 计算显示Au(I)配合物对C2H4氢化具有较好的催化效果, 其作用下的加氢反应存在“活化H―H键后再与C2H4反应”和“活化C=C键后再与H2反应”两种途径, 前者的活化能较后者低90-120 kJ·mol-1, 因而具有明显的能量优势. 研究表明AuPR3+ 的催化能力明显强于AuX. 此外, X/PR3基团供、吸电子能力的变化对配合物的催化能力也具有较为显著的影响. 电子结构分析显示Au(I)配合物在C2H4 加氢反应中不仅能够削弱H―H、C=C 键的强度, 还使H2 σH―H*、C2H4 πC=C* 轨道能级下降, 从而缩小了πC=CH―H*或σH―HC=C*轨道间的能级差, 促进了C2H4-H2反应中的电子离域, 从而降低禁阻反应发生的难度.σH―H*、πC=C*轨道能级改变量与加氢反应活化能Ea的降低值之间存在较好的一致性关系, 因此使上述轨道能级下降幅度越大的Au(I)配合物可以获得较好的催化效果.  相似文献   

11.
12.
The binding mechanism between 9-vinyladenine and pyrimidine base thymine in methanol was studied with UV-visible spectrophotometric method. Based on this study, using thymine as a template molecule, 9-vinyladenine as a novel functional monomer and diethylene glycol dimethacrylate as a new cross-linker, a specific diethylene glycol dimethacrylate-based molecularly imprinted polymeric membrane was prepared over a cellulose support. Then, the resultantly polymeric membrane morphologies were visualized with scanning electron microscopy and its permselectivity was examined using thymine, uracil, cytosine, adenine and guanine as substrates. This result showed that the imprinting polymeric membrane prepared with diethylene glycol dimethacrylate exhibited higher transport capacity for the template molecule thymine and its optimal analog uracil than other nucleic acid bases. The membrane also took on higher permselectivity than the imprinted membrane made with ethylene glycol dimethacrylate as a cross-linker. When a mixture including five nucleic acid bases thymine, uracil, cytosine, adenine and guanine passed through the diethylene glycol dimethacrylate-based thymine-imprinted polymeric membrane, recognition of the membrane for the template molecule thymine and its optimal analog uracil was demonstrated. It was predicted that the molecularly imprinted membrane prepared with diethylene glycol dimethacrylate as cross-linker might be applicable to thymine assay of absolute hydrolysates of DNA or uracil assay of absolute hydrolysates of RNA in biological samples because of its high selectivity for the template molecule thymine and its optimal analog uracil.  相似文献   

13.
Semiclassical dynamics simulation is used to study dimerization of two stacked cytosine molecules following excitation by ultrashort laser pulses (25 fs fwhm, Gaussian, 4.1 eV photon energy). The initial excited state was found to form an ultrashort exciton state, which eventually leads to the formation of an excimer state by charge transfer. When the interbase distance, defined as an average value of C(5)-C(5)' and C(6)-C(6)', becomes less than 3 ?, charge recombination occurs due to strong intermolecular interaction, eventually leading to an avoided crossing within 20-30 fs. Geometries at the avoided crossing, with average intermolecular distance of about 2.1 ?, are in accord with CASSCF/CASPT2 calculations. Results indicate that the C(2)-N(1)-C(6)-C(5) and C(2)'-N(1)'-C(6)'-C(5)' dihedral angles' bending vibrations play a significant role in the vibronic coupling between the HOMO and LUMO, which leads to a nonadiabatic transition to the electronic ground state.  相似文献   

14.
Interactions of adenine, cytosine, guanine, and thymine with Na(+), Mg(2+), and Zn(2+) cations were studied using an approximate resolution of identity correlated second-order MP2 (RI-MP2) method with the TZVPP ([5s3p2d1f/3s2p1d]) basis set. All existing tautomers of adenine, cytosine, and thymine and the eight most stable keto/enol tautomers of guanine were considered. Cations bind mostly in a bidentate manner, and stabilization energies of these complexes are larger than those in the case when cations bind in a unidentate manner. The cation...Y (Y equal to N or O) distances for divalent metals are shorter than those for Na(+) and for Zn(2+) are mostly shorter than the Mg(2+)...Y distance. The intermolecular distances between the cation and the base for complexes containing adenine and cytosine are systematically shorter than those for complexes containing guanine and thymine. Only for cytosine the canonical keto/amino tautomer structure with ions represents the global minimum. For guanine, the metalated canonical form is again the most stable, but its stabilization energy is within less than 5% of the stabilization energies of the two other rare tautomers, which indicates that the canonical form and these two rare tautomers could coexist. The canonical structures of adenine and thymine in the presence of ions are considerably less stable (by more than 10%) than the complexes of the rare tautomers. It can be concluded that the interaction of Na(+), Mg(2+), and Zn(2+) cations with cytosine in the gas phase will not induce the change of the canonical form to the rare tautomeric form. In the case of isolated guanine, the equilibrium of the canonical form with rare tautomers can be found. For isolated adenine and thymine the presence of rare tautomers is highly probable.  相似文献   

15.
设计合成了含氮杂冠醚和胸腺嘧啶的双亲聚合物聚[N,N-二乙氧基-1,10-二氮杂-18冠-6-5-甲基-胸腺嘧啶-异酞酸酯](PCTSE).用SEM观测到其在水溶液中自发聚集成直径为150~220nm的纳米球;用动态光散射测得PCTSE纳米球水溶液的粒径分布主要集中在130~240nm,用FTIR研究了PCTSE/腺嘌呤中胸腺嘧啶与底物腺嘌呤的分子识别作用,结果表明,聚合物中胸腺嘧啶环上C4O伸缩振动峰从1670cm-1位移至1664cm-1,表明胸腺嘧啶与腺嘌呤间形成了氢键.变温红外光谱表明,该峰又随温度的升高逐渐向高波数位移,最后位移到识别前的1670cm-1处,表明所形成的氢键断裂.  相似文献   

16.
A study of the minor-groove recognition of A/T-rich DNA sites by Ni(II).L-Arg-Gly-His and Ni(II).D-Arg-Gly-His was carried out with a fluorescence-based binding assay, one- and two-dimensional (1D and 2D) NMR methodologies, and molecular simulations. Fluorescence displacement titrations revealed that Ni(II).L-Arg-Gly-His binds to A/T-rich sequences better than the D-Arg diastereomer, while NMR investigations revealed that both metallopeptides bind to the minor groove of an AATT core region as evidenced by an intermolecular nuclear Overhauser effect (NOE) between each metallopeptide His imidazole C4 proton and the C2 proton of adenine. Results from molecular dynamics simulations of these systems were consistent with the experimental data and indicated that the His imidazole N-H, the N-terminal peptide amine, and Arg side chains of each metallopeptide are major determinants of minor-groove recognition by functioning as H-bond donors to the O2 of thymine residues or N3 of adenine residues.  相似文献   

17.
The present paper highlights results of a systematic study of photoinduced electron transfer, where the fundamental aspects of the photochemistry occurring in solutions and in artificially or self-assembled molecular systems are combined and compared. In photochemical electron transfer (ET) reactions in solutions the electron donor, D, and acceptor, A, have to be or to diffuse to a short distance, which requires a high concentration of quencher molecules and/or long lifetimes of the excited donor or acceptor, which cannot always be arranged. The problem can partly be avoided by linking the donor and acceptor moieties covalently by a single bond, molecular chain or chains, or rigid bridge, forming D-A dyads. The covalent combination of porphyrin or phthalocyanine donors with an efficient electron acceptor, e.g. fullerene, has a two-fold effect on the electron transfer properties. Firstly, the electronic systems of the D-A pair result in a formation of an exciplex intermediate upon excitation both in solutions and in solid phases. The formation of the exciplex accelerates the ET rate, which was found to be as fast as >10(12) s(-1). Secondly, the total reorganization energy can be as small as 0.3 eV, even in polar solvents, which allows nanosecond lifetimes for the charge separated (CS) state. Molecular assemblies can form solid heterogeneous, but organized systems, e.g. molecular layers. This results in more complex charge separation and recombination dynamics. A distinct feature of the ET in organized assemblies is intermolecular interactions, which open a possibility for a charge migration both in the acceptor and in the donor layers, after the primary intramolecular exciplex formation and charge separation in the D-A dyad. The intramolecular ET is fast (35 ps) and efficient, but the formed interlayer CS states have lifetimes in microsecond or even second time domain. This is an important result considering possible applications.  相似文献   

18.
A systematic study of structures and electronic properties has been carried out for the nucleic acid bases adenine, guanine, thymine, and cytosine and for the base pairs adenine–thymine and guanine–cytosine. We focus our attention on these properties, which experience significant changes when single nucleic bases join to form base pairs. Such properties are expected to play an important role during the formation of the DNA molecule in its B conformation. All-electron calculations with inclusion of correlation effects were performed according to the local and nonlocal density functional approaches. We compare our results with previous ab initio and semiempirical values and with available experimental data. Advantages and disadvantages for these density functional-based methods are discussed. We conclude that applications of such models to investigate larger compounds of a similar nature are promising. © 1994 by John Wiley & Sons, Inc.  相似文献   

19.
采用半经典动力学方法模拟了激光诱导下π堆积的腺嘌呤体系最低激发态的失活过程. 模拟激光脉冲仅作用于一个腺嘌呤分子. 发现随着激发态腺嘌呤分子(A)与基态腺嘌呤分子(A′)之间距离的缩短, 它们的相互作用显著增强. 分子间的相互作用导致了一条新的失活通道, 即C2原子与C2′原子靠拢成键, 形成“成键的激基复合体”的中间体. 中间体的寿命约为390 fs. C2原子的畸变和H2′原子的环面外振动导致中间体失活. 失活后C2-C2′断裂, 释放的键能转化为分子动能, 腺嘌呤分子恢复基态的平面结构.  相似文献   

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