环草酰胺表面增强拉曼光谱密度泛函理论研究

根据密度泛函理论(DFT),在B3LYP方法下,Ag原子使用LANL2DZ赝式基组,C,H,N,O和Cl原子使用6-31++G(d,p)基组,优化并计算了环草酰胺和环草酰胺银配合物的拉曼光谱,并利用密度泛函理论对环草酰胺分子拉曼光谱及其SERS进行详细归属,为食品和产品中吩噻嗪残留的定性、定量测定提供理论依据。计算结果说明连接Ag原子越多,增强效果越明显。     

2,6-二氯苯硫代甲酰胺的表面增强拉曼光谱密度泛函理论研究

根据密度泛函理论,在B3LYP方法下,Ag原子使用LANL2DZ赝式基组,C,H,N,S,Cl原子使用6-31++G(d,p)基组,计算了2,6-二氯苯硫代甲酰胺及其银配合物的拉曼光谱,并利用GaussianView对2,6-二氯苯硫代甲酰胺分子及SERS进行详细归属,为食品和产品中2,6-二氯苯硫代甲酰胺残留的表面增强拉曼光谱测定提供理论依据。     

甲萘威的表面增强拉曼光谱密度泛函理论研究

根据密度泛函理论,在B3LYP方法下,Ag原子使用LANL2DZ赝式基组,C,H,N,O原子使用6-31++G(d,p)基组,计算了甲萘威及其银配合物的拉曼光谱,并利用GaussianView对甲萘威分子及SERS进行详细归属,为农产品和环境监测中甲萘威残留的表面增强拉曼光谱测定提供理论依据。     

双三氟虫脲表面增强拉曼光谱的密度泛函理论研究

在密度泛函理论下使用6-31++G(d,p)基组对基态的双三氟虫脲进行结构优化和振动频率的计算。对Ag-BTF,Ag_2-BTF,Ag_3-BTF,Ag_4-BTF所有的配合物在B3LYP方法下使用6-31++G(d,p)(C,H,N,O,F,Cl)基组以及Lanl2dz(Ag)赝氏基组进行结构优化和振动光谱的计算。并对14号和18号氮原子分别进行配位。计算结果显示表面增强的效果依赖于银原子连接的位置以及个数。银原子数连接的越多,增强效果越明显。     

反式乙烯基联吡啶表面增强拉曼光谱的密度泛函理论研究

反式乙烯基联吡啶具有极好的拉曼散射信号,经常用做探针分子.利用密度泛函理论(DFT)理论,采用BP86,BPw91和B3LYP等方法,Ag原子使用赝式基组,H,C,N等原子使用6-31+ +G(d,p)基组,计算了反式乙烯基联吡啶与银配合物(t-BPE-Ag)的Raman光谱,并且利用势能分布(PED)计算结果对t-BPE分子Raman光谱和SERS谱进行了详细的归属,DFT理论得到结果说明根据DFT理论计算t-BPE-Ag配合物得到的Raman光谱与实验SERS谱基本一致,并且键连Ag原子越多,与实验值会更接近,t-BPE-Ag配合物HOMO与LUMO的能级差估计在449～912 nm范围内.     

亚甲基蓝在胶体银表面的吸附——表面增强拉曼光谱和密度泛函理论计算

获得了不同浓度下亚甲基蓝(methylene blue,MB)溶液在银溶胶中的表面增强拉曼光谱。结果表明： 亚甲基蓝分子与银纳米粒子高浓度下物理吸附为主,低浓度下化学吸附为主;不同浓度下存在不同的吸附取向,即高浓度下为“直立”取向,低浓度为“平躺”取向。通过观察低浓度下MB在银胶中吸附时间对谱图的影响,得知低浓度下吸附取向不随时间发生变化。应用密度泛函(DFT)方法在B3LYP/6-31+G*和LANL2DZ基组水平上对亚甲基蓝阳离子(MB+)及MB+与Ag原子形成的不同构型体系进行了结构优化和频率计算。实验与理论计算结果表明,MB+有可能通过N—Ag和S—Ag与Ag原子形成两种较强的吸附构型。电荷布居分析表明,与S原子相比,芳香环上的N原子更易与Ag发生相互作用。还对实验观察到的部分谱峰及它们的振动模式作出了初步归属和讨论。     

西玛津表面增强拉曼光谱的密度泛函理论研究

利用Gaussian09程序及密度泛函理论,采用B3LYP方法对C,N,H,Cl原子运用6-31++G基组进行计算,对Ag原子采用赝势基组Lan12dz计算,并对计算出的西玛津及其配合物的拉曼光谱进行指认和归属,为研究西玛津在土壤与食品中的残留检测提供理论依据。     

AlH分子结构与分析势能函数

本文运用群论及原子分子反应静力学方法,推导了 AlH分子的基态(X1Σ+)、第一激发态(A1Π)及第三激发态(C1S+)的电子态及相应的离解极限.并使用SAC/SAC-CI方法,采用D95 (d)、6-311g(d)和cc-PVTZ等基组对AlH分子的基态(X1Σ+)、第一激发态(A1Π)和第三激发态(C1S+)的平衡结构和谐振频率进行了几何优化计算.通过对三个基组的计算结果与实验结果的比较,得到cc-PVTZ基组是三个基组中最优基组的结论.使用cc-PVTZ基组,对AlH 分子的基态(X1Σ+)、第一激发态(A1Π)和第三激发态(C1S+)进行了单点能扫描计算,并给出了AlH的基态(X1Σ+)、第一激发态(A1Π) 和第三激发态(C1S+)的Murrell-Sorbie函数形式的电子态的完整势能函数,进而得到了AlH分子第一激发态(A1Π)的激发能较小的结论.     

TiN分子基态(X~2∑)结构和势能函数

应用群论及原子分子反应静力学方法推导了TiN分子基态(x~2∑)的离解极限.采用不同的密度泛函方法,包括BP86,B3P86,B3Lyp,B3PW91,分别选用不同的基组对TiN分子基态进行结构优化计算.通过比较得出使用BP86方法,对N原子使用D95V++(d,P)基组和Ti原子使用6-311++G~()基组时,计算得到的平衡几何结构、分子离解能和谐振频率与实验值符合得最好.并采用最小二乘法拟合改进的Murrell-Sorbie函数得到了相应电子态的完整势能函数.计算得到的光谱常数与实验光谱数据符合得很好.     

噻虫啉的表面增强拉曼光谱密度泛函理论研究

依据DFT理论的B3LYP方法下,在6-31G(d,p)(C,H,N,S,Cl)/Lanl2dz(Ag)基组,计算得到噻虫啉及其银配合物的稳定结构和表面增强拉曼光谱(SERS)。并进一步探究SERS与Ag4银簇吸附的位置,分子分别以单端(吡啶氮/氰基)和双端(吡啶氮和氰基)与Ag4银簇吸附。通过比较,TPD在双端吸附银簇下比单端(吡啶氮/氰基)吸附下的SERS(频率)更符合实验值。     

含吩噻嗪及其衍生物的聚合物有机电致发光材料的合成和器件制备

利用吩噻嗪单体的空穴传输能力、吩噻嗪衍生物单体的拉电子特性和它们分子结构的非共面性,制备了高效的含吩噻嗪及其衍生物结构单元的对苯撑乙烯聚合物有机电致发光材料P1。同时在单体中引入了烷氧基和长链烷基,使得合成的聚合物在四氢呋喃、氯仿、二氯甲烷、甲苯等溶剂中有较好的溶解性。研究吩噻嗪衍生物单体的拉电子特性对聚合物P1的电子传输性能的影响,合成不含吩噻嗪衍生物的同一类型聚合物P2。制备以聚合物P1和P2为发光层的单层OLED器件,经测量,聚合物P1的器件外量子效率是聚合物P2器件的3.5倍。     

Electronic Spectral Studies and Determination of the First Excited Singlet-State Dipole Moments of New Benzo[a]phenothiazine Derivatives

The room temperature (298 K) electronic absorption, and fluorescence excitation and emission spectra of seven new, pharmacologically-important benzo[a]phenothiazines (12H-benzo[a]phenothiazine ( 1 ), 9-methyl-12H-benzo[a] phenothiazine ( 2 ), 10-methyl-12H-benzo[a] phenothiazine ( 3 ), 11-methyl-12H-benzo[a]phenothiazine ( 4 ), 5-oxo-5H-benzo[a]phenothiazine ( 5 ), 6-hydroxy-5-oxo-5H-benzo[a]phenothiazine ( 6 ) and 6-methyl-5-oxo-5H-benzo[a] phenothiazine ( 7 ):) were measured in several solvents of different polarities and hydrogen bonding abilities. In combination with the ground state dipole moments of these benzo[a]phenothiazines, the spectral data were used to determine their first excited singlet-state dipole moments by means of the solvatochromic shift method. These excited singlet-state dipole moments were found to be significantly higher (1.9 to 2.5 Debye units) than their ground-state counterparts.     

吩噻嗪卤代衍生物的荧光研究

本文主要研究了3-溴-N-乙基吩噻嗪(Br-P)在各种酸度、增敏溶剂、感光效应等条件下的荧光变换现象，并确定了最佳的发光体系。方法简单、准确可靠，其线性范围为1×10     

A first-principles study of π-conjugated thiol phenothiazine derivatives adsorbed on Au(111) surface

We present an extensive theoretical study of a series of phenothiazine derivatives adsorbed on Au(111). A series of experimentally accessible quantities are calculated (ultra-violet photoemission spectra, scanning tunneling microscopy images). All simulations were performed by using DFT techniques and LCAO expansion of the molecular orbitals. The microscopic picture established in this work provides a deeper understanding of the interfacial processes that govern the working principle of single-molecule electronics and organic electronic devices.      

2,3,7,8—四氯代—N—乙基吩噻嗪的荧光法研究

本文研究了２，３，７，８－四氯代－Ｎ－乙基吩噻嗪在不同条件下的荧光强度变化规律，为荧光体确定了最佳发光体系，对提高有机光导体的灵敏度具有实际意义。     

Antioxidant effects of phenothiazine,phenoxazine, and iminostilbene on free‐radical‐induced oxidation of linoleic acid and DNA

Antioxidant effects of phenothiazine (PtzNH), phenoxazine (PozNH), and iminostilbene (IsbNH) on the oxidation of linoleic acid (LH) and DNA induced by 2,2′‐azobis(2‐amidinopropane) dihydrochloride (AAPH) were investigated in this work. LH was suspended in the liposome of dipalmitoyl phosphatidylcholine (DPPC) to mimic a biomembrane. In the course of AAPH‐induced oxidation of LH, the inhibition period (t_inh) generated by PtzNH, PozNH, and IsbNH was proportional to the concentrations of PtzNH, PozNH, and IsbNH employed. The abilities of PtzNH, PozNH, and IsbNH to protect LH were similar to that of trolox (6‐hydroxyl‐2,5,7,8‐tetramethylchroman‐2‐carboxylic acid). Quantum chemical calculations elucidated that the nonplanar configurations of PtzNH, PozNH, and IsbNH transformed to planar ones when they were converted into radicals. In addition, spin‐densities (SDs) on the N atom in the radicals derived from PtzNH, PozNH, and IsbNH were calculated. The N atom in the radical of PtzNH possessed the lowest SD, indicating that the radical of PtzNH was the most stable one. Moreover, PtzNH, PozNH, and IsbNH were applied to protect the DNA against AAPH‐induced oxidation, in which PozNH and IsbNH were able to generate t_inh. The t_inh generated from PozNH and IsbNH was also proportional to their concentrations. The antioxidant effect of PozNH on the oxidation of DNA was higher than that of IsbNH. Copyright © 2009 John Wiley & Sons, Ltd.     

Reverse phenomena of magnetic field effects and time-resolved EPR spectra in the photogenerated biradical from intramolecular electron-transfer in a phenothiazine–C60 linked compound with a semi-rigid spacer

Photoinduced electron-transfer reactions and magnetic field effects (MFEs) on the decay rates of the photogenerated biradical in a phenothiazine (Ph)–C₆₀ linked compound with a biphenyl group (Ph(BP)C₆₀) were examined in benzonitrile and benzene. Fluorescence and transient absorption spectra indicate that the intramolecular electron-transfer for Ph(BP)C₆₀ from the Ph to the singlet or triplet excited state of C₆₀ was suppressed by the biphenyl group. The decay rates of the photogenerated biradical decreased in the 0–0.2 T magnetic field range and increased in the 0.2–1 T magnetic field range. The reverse phenomena of the MFEs in Ph(BP)C₆₀ were strongly enhanced with increasing temperature and similar to those in Ph(n)C₆₀ (n = 6?12). The MFEs in Ph(BP)C₆₀ can be governed by spin-lattice relaxation and/or spin-spin relaxation mechanisms as observed in Ph(n)C₆₀ (n = 6?12). Time-resolved EPR spectra of Ph(BP)C₆₀ showed absorption, emission, absorption and emission patterns, and are quite different from those in Ph(n)C₆₀ (n = 4?12). The result indicates that the magnitude and distribution of the exchange interaction |2J| in Ph(BP)C₆₀ are smaller than those in Ph(n)C₆₀ (n = 4?12) and charge recombination occurs in the inverted region because the sign of the J is positive.     

Rational design and first-principles studies of phenothiazine-based dyes for dye-sensitised solar cells

We investigate a series of phenothiazine (PT)-based organic dyes by adopting different donors and different donor substitution positions as photosensitisers for application in dye-sensitised solar cells (DSSCs). First-principles calculations reveal systematic improvements of key parameters including light-harvesting efficiency, redox potential, electron injection and non-linear optical properties with donor substitutions. The non-planar structure also suppresses dye aggregation and reduces the rate of internal charge recombination. In particular, photosensitisers with combination of donor functional groups show outstanding performance on these key parameters. This study demonstrates that PT-based dyes with the studied donor groups could serve as excellent candidates of photosensitisers for future DSSC applications.     

氢键效应对2,3-二氢-3-酮基-1H-吡啶并[3,2,1-kl]吩噻嗪光物理性质的影响

利用含时密度泛函理论(TDDFT)方法和飞秒时间分辨的瞬态吸收光谱技术对2,3-二氢-3-酮基-1H-吡啶并[3,2,1-kl]吩噻嗪(PTZ4)和3-酮基-1H-吡啶并[3,2,1-kl]吩噻嗪(PTZ5)这两种荧光探针分子的光物理性质进行了研究. TDDFT结果表明PTZ4和PTZ5在甲醇溶液形成了氢键络合物导致它们吸收峰的红移. PTZ4分子在基态有四种稳定构型,其在四氢呋喃溶液中的双荧光峰正是来自于四种构型下的内部电荷转移态. PTZ4分子在四氢呋喃和甲醇溶液中的瞬态吸收光谱表明,从局域态到转移态的弛豫时间常数在四氢呋喃中为16.0 ps,在甲醇中为7.5 ps;PTZ4分子在甲醇中的激发态寿命为53.8 ps,而这种超短的寿命可能是由于PTZ4分子在激发态时形成的面外型氢键络合物导致的.     

Theoretical analysis and simulation of conjugate heights for dual-conjugate AO system in lidar

A multi-conjugate adaptive optics （MCAO） can offer a possibility of widening field of view （FOV） characterized by the isoplanatic angle, and the choose of conjugate height becomes a basic problem for MCAO, which influences the size of iosplanatic angle. Considering the application of lidar, the isoplanatic angle＇s expressions of two deformable mirrors （DMs） MCAO for uplink and downlink are deduced. The effects of conjugate heights for dual-conjugate AO are thoughtfully discussed, and the isoplanatic angles are further analyzed. The results show that the isopanatic angle varies with the conjugate height and reaches the maximum as the conjugate height is at the optimal altitude. Moreover, the optimal conjugate height changes with the propagation distance.