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1.
采用共振拉曼光谱和完全活化空间自洽场方法研究了N,N-二甲基硫代乙酰胺在被激发至S3(ππ*)态后的衰减动力学. 指认了紫外吸收光谱和振动光谱. 获得了乙腈、甲醇和水溶剂中不同激发波长下的A带共振拉曼光谱,以探测Franck-Condon区域的结构动力学. 开展了CASSCF计算以确定低能单重激发态和锥形交叉点的电子激发能和优化几何结构. 通过共振拉曼强度分析和CASSCF计算获得了结构参数、A带结构动力学和S3(ππ*)态衰减机制. 提出了主要衰减通道为3,FC(ππ*)→S3(ππ*)/S1(nπ*)→1(nπ*).  相似文献   

2.
采用共振拉曼光谱学和完全活化空间自洽场方法研究了苯基叠氮被激发到S2(A')、S3(A')和S6(A')光吸收态后的结构动力学. 基于傅立叶变换拉曼、傅立叶变换红外、紫外、密度泛函计算和简正模式分析,指认了紫外吸收光谱和振动光谱. 获得了环己烷、乙腈和甲醇溶剂中273.9、252.7、245.9、228.7、223.1和208.8 nm等不同激发波长下的A、B和C带共振拉曼光谱,以探测Franck-Condon区域的结构动力学. CASSCF计算获得了单重电子激发态能量最低点和势能面交叉点的电子激发能和优化几何结构. 结果表明,苯基叠氮在S2(A')、S3(A')和S6(A')态上的激发态结构动力学各不相同. 与Kasha规则相符,S2S1(1)和S2S1(2)势能面交叉点在S2(A')激发态衰变动力学和N7=N8键解离中扮演着重要角色. 提出了两条主要衰减通道:S2,min→S0辐射通道和S2,FC(ππ*)→S2(ππ*)/S1(nπ*)→S1(nπ*)非辐射通道.  相似文献   

3.
用密度泛函理论B3LYP方法和6-311G(d,p)/Lanl2DZ优化得到黄曲霉素B1(AFB1)分子及其复合物AFB1-Ag的稳定结构,并计算了复合物的表面增强拉曼光谱和预共振拉曼光谱. 结果表明,AFB1分子的拉曼光谱很大程度依赖于吸附位点以及入射光的激发波长. 与分子的常规拉曼光谱相比,复合物表面增强拉曼光谱中C=O伸缩振动模的增强因子约为102~103复合物的极化率增强而导致的静态化学增强,并分析了振动模式的振动方向与其拉曼强度的关系.选择复合物最大吸收峰附近激发光266和482 nm以及远离共振吸收波长785和1064 nm作为入射光,计算得到不同入射光激发下复合物的预共振拉曼光谱.结果表明其增强因子最大达到104量级,主要是由电荷转移产生的共振增强引起的.  相似文献   

4.
激发态双质子转移反应长期困扰着理论和实验科学家并成为了一个悬而未决的热点问题. 本文利用完全活化空间自洽场方法及其二阶微扰理论(MS-CASPT2//CASSCF)系统地研究了典型体系1,8-二羟基-2-萘甲醛(DHNA)的激发态双质子转移反应以及相关的激发态弛豫过程. 在MS-CASPT2//CASSCF水平下,本文优化了三个能量相近但结构不同的S1态互变异构体,即S1-ENOL、S1-KETO-1和S1-KETO-2,以及两个关键的S1/S0锥形交叉点结构,即S1S0-KETO-1和S1S0-KETO-2. 其中,两个极小点S1-KETO-1和S1-KETO-2与实验上观测到的双荧光发射现象密切相关. 本文还利用MS-CASPT2//CASSCF方法计算了双质子转移反应的二维势能面以及从极小点到交叉点结构的线性内插路径;相应计算结果证实了DHNA体系具有分步的激发态双质子转移机制. 具体来说,从S1-ENOL到S1-KETO-1的第一个质子转移过程是无能垒的,而从S1-KETO-1到S1-KETO-2的第二个质子转移过程则需要克服一个大约6.0 kcal/mol的能垒. 此外,由于从S1-KETO-1 (S1-KETO-2)到S1S0-KETO-1 (S1S0-KETO-2)的线性内插路径显示DHNA体系需要翻越一个约为12.0 kcal/mol的能垒,因此DHNA体系将在S1态上停留一段时间并发生双荧光发射现象. 当然,S1/S0锥形交叉点也会促使DHNA体系从S1态内转换到S0态,而这会一定程度上降低DHNA体系发射荧光的效率. 可以通过限制C5-C8-C9-O10二面角旋转来降低体系的内转换效率,进而提高DHNA体系的发光效率. 本工作不仅有助于理解激发态双质子转移机制,还有助于设计具有优异发光性能的新型分子材料.  相似文献   

5.
本文利用神经网络方法构建了苯硫酚三维的基态(S0)绝热势能面以及激发态1ππ*1πσ*耦合的非绝热势能面. 特别地,1ππ*1πσ*非绝热势能面的透热化是通过神经网络拟合实现的,拟合仅基于其绝热势能,但对非绝热势能矩阵的非对角元施加了对称性的正确限制. 神经网络拟合的3个态的势能面的拟合均方根误差都非常小(<4 meV),体现了神经网络方法的高精度. 在神经网络构建的势能面上计算得到了S0态的低位能级和S1 态00 的寿命,结果均与早前非绝热势能面上的结果吻合,验证了神经网络方法构建的绝热和非绝热势能面的高精度和可靠性.  相似文献   

6.
陈琳  汪蕾  郑敏  王琳 《化学物理学报》2021,34(2):188-196
本文利用纳秒瞬态吸收光谱技术,在不同溶剂中,研究了噻吨酮的光物理和光化学行为. TX的激发三重态(3TX*)涉及2种电子态,3*3ππ*态. 随着溶剂极性的增强,3ππ*态的贡献加大. 在CH3CN,CH3CN/CH3OH(1:1)和CH3CN/H2O(1:1)溶剂中,3TX*的自猝灭速率常数ksq逐渐减小. 这可能由于通过氢键形成的激基复合物阻碍了3TX*的碰撞猝灭. 二苯胺通过电子转移还原3TX*,生成TX·-阴离子和DPA·+阳离子自由基. 溶剂对该转移过程的影响不明显,表明TX的3*3ππ*态夺取电子的能力相近. 然而,溶剂的依赖性在TX·-的猝灭过程中表现明显. 在强酸性条件下(pH=3.0),质子化的TX和非质子化的TX之间存在着动态平衡. 在激发光作用下,生成3TXH+*,光谱上呈现出520 nm处的吸收峰.  相似文献   

7.
The processes of excitation transfer from the 82S1/2 state to the 62D state of rubidium in Rb(82S1/2)-Rb(52S1/2) and Rb(82S1/2)-H2 collisions have been studied experimentally. During irradiating the Rb vapor, mixed with H2, by two light beams for selective stepwise excitation, the Rb 82S1/2→52P3/2 direct fluorescence and the Rb 62D3/2→52P1/2 sensitized fluorescence have been measured as a function of H2 gas pressure. The measurements yielded the cross-sections σ(82S1/2→62D) and σ*(82S1/2→62D) of Rb 82S1/2→62D excitation tranfer induced by collisions with 52S1/2 atom and H2 molecules respectively. The results are discussed in detail.  相似文献   

8.
The processes of excitation transfer from the 82S1/2 state to the 62D state of rubidium in Rb(82S1/2)-Rb(52S1/2) and Rb(82S1/2)-H2 collisions have been studied experimentally. During irradiating the Rb vapor, mixed with H2, by two light beams for selective stepwise excitation, the Rb 82S1/2→52P3/2 direct fluorescence and the Rb 62D3/2→52P1/2 sensitized fluorescence have been measured as a function of H2 gas pressure. The measurements yielded the cross-sections σ(82S1/2→62D) and σ*(82S1/2→62D) of Rb 82S1/2→62D excitation tranfer induced by collisions with 52S1/2 atom and H2 molecules respectively. The results are discussed in detail.  相似文献   

9.
本文求出了Eliashberg方程在T=Tc时的解,得到了下面的临界温度级数表示式:Tc0*)(λ〈ω2〉)1/2{1+1/λα1*)〈ω4>/〈ω2>2+1/λ221*)〈ω6>/〈ω2>322*)〈ω4>2/〈ω2>4) +1/λ331*)〈ω8>/〈ω2>432*)(〈ω4>〈ω6>)/〈ω2>5)+α33*)〈ω4>3/〈ω2>6+…},其中α0*),α1*)等仅是μ*的函数。新的Tc公式表明了,Tc不仅依赖于λ、μ*和〈ω2〉,而且依赖于有效声子谱α2F(ω)的各级矩〈ω2n〉。  相似文献   

10.
利用脉冲激光溅射-超声分子束载带方法制备了气相Ti+(CO2)2Ar和Ti+(CO2)n(n=3-7)络合物离子.采用红外光解离光谱研究了这些选定的质量离子的振动光谱. 对于每一种络合物离子, 在CO伸缩振动频率范围都观察到了振动峰,表明这些离子具有插入的OTi+CO(CO2)n-1结构. 对于n≦5的OTi+CO(CO2)n-1离子,其CO振动和CO2的反对称伸缩振动频率都比自由的CO和CO2的频率要高,表明CO和CO2配体与中心金属离子之间主要是静电相互作用.实验结果还表明TiO+可以直接络合五个配体(1个CO和4个CO2分子).对于n=2络合物体系,除了插入的OTi+CO(CO2)结构以外,还观察到了具有弯曲结构的OCO-Ti+-OCO异构体的存在  相似文献   

11.
Two-dimensional scanning of a 0.6328 mum guided-light beam has been realized using noncolinear acousto-optic (AO) coplanar Bragg diffraction together with colinear AO guided-mode to substrate radiation-mode conversion in a Z-cut Xpropagation LiNbO3 proton-exchanged (PE) waveguide. The two surface acoustic (SAW) waves utilized are at the center frequencies of 500 and 200 MHz, propagating in the Y and X axes, respectively. Two-dimensional scanning of approximately 720 resolvable light beam spots, namely, 18 40 (horizontal vertical) scanning, has been demonstrated using a light beam of 1.0 mm aperture. The total number of resolvable beam spots can be greatly increased from 720 by simply utilizing SAW transducers of larger bandwidth and a light beam of greater aperture. It should also be possible to significantly increase the diffraction efficiency from 3 % by optimizing the parameters of the PE waveguide and the SAWs.  相似文献   

12.
A simple technique of pulse compression, based on the linear chirp compensation of self-phase modulation (SPM) spectra in dispersion shifted fibers, is demonstrated. The optimization procedure is carried out, for a short span of a single-mode fiber, using a parabolic law, which describes the behavior of the squared output pulse width versus the pump peak power in the case of Gaussian pulses. The experimental results give a minimum pulse duration of 233 fs, which is in good agreement with the model. Shorter and coherent pulses, down to 90 fs, have been obtained by inserting an interference filter at the optical output.  相似文献   

13.
A review of schemes for multiple access in fiber optic networks shows that a hybrid of wavelength and code division multiple access (WCDMA) combines the best features of both. In particular, the hybrid scheme retains the large information carrying capacity of wavelength division multiple access (WDMA) and flexibility of code division multiple access (CDMA). In this paper WDMA, optical CDMA (OCDMA), and WCDMA networks are discussed. In OCDMA networks, concept of incoherent and coherent coding including inverse decoding and matched filter is introduced. The delay performance of both WDMA and WCDMA networks, under the simple suboptimum access protocols based on cyclic search, is computed. It has been shown quantitatively that tuning delay significantly affects the delay performance of both WDMA and WCDMA networks. Futhermore, delay performance of WCDMA networks is always better than the WDMA networks for the same tuning delay, load, and number of users.  相似文献   

14.
Results of a study of the effect of γ-radiation on the spectral luminescence properties of cadmium tungstate crystals doped with silver, bismuth, and molybdenum cations are presented. Spectral characteristics of the nondnnnoped crystals are briefly described. Absorption and photo and X-ray luminescence spectra of the crystals taken before and after exposure to γ-radiation (5.5·104 Gy) are compared. It is found that the spectral characteristics of the crystals doped with silver, bismuth, and molybdenum cations do not change markedly after the exposure. The relation between the type of impurity-induced defects, individual characteristics of the impurity cations, and the character of the effect of γ-radiation on the spectral luminescence properties of impure crystals is analyzed (preliminarily). Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 1, pp. 55–60, January–February, 1997.  相似文献   

15.
The Shanghai Synchrotron Radiation Facility(SSRF)booster ring,a full energy injector for the storage ring,is deigned to accelerate the electron beam energy from 150MeV to 3.5GeV that demands high extraction efficiency at the extraction energy with low beam loss rate when electrons are ramping.Closed orbit distortion(COD)caused by bending magnet field uniformity errors which affects the machine performance harmfully could be effectively reduced by bending magnet location sorting.Considering the affections of random errors in measurement,both ideal sorting and realistic sorting are studied based on measured bending magnet field uniformity errors and one reasonable combination of bending magnets which can reduce the horizontal COD by a factor of 5is given as the final installation sequence of the booster bending magnets in this paper.  相似文献   

16.
17.
A transient suppression method for piezoelectric ceramic transducer is presented. By adding some special pedestal pulses to the original transmitted signal, the transient effects in the output of the transducer can be just precisely transmission by use of a narrowband transducer. canceled, thereby achieving the broadband The experimental results show that the transient responses of the sinusoid pulses and coded signals are suppressed successfully and the acoustic waveforms radiated into the surrounding water are improved significantly.  相似文献   

18.
We experimentally demonstrate amplitude squeezed soliton utilizing intensity-dependent self-phase modulation in an asymmetric Sagnac interferometer.The system.whose components are connected via ferrule connector/physical connection(FC/PC)fiber connectors,constitutes all-fiber configuration to generate squeezed soliton.Soliton amplitude reduction measured by homodyne detection is near 4.0 dB below the shot-noise level.Optimal squeezing fields in both simple and compact all-fiber configuration are obtained.  相似文献   

19.
The(2 1)-dimensional nonlinear Schr(o)dinger(NLS)equation with spatially inhomogeneous nonlinearities is investigated,which describes propagation of light in(2 1)-dimensional nonlinear optical media with inhomogeneous nonlinearities.New types of optical modes and nonlinear effects in optical media are presented numerically.The results reveal that the regular split of beam can be obtained in (2 1)-dimensional nonlinear optical media with inhomogeneous nonlinearities,by adjusting the guiding parameter.Furthermore,the stability of beam regular split is discussed numerically,and the results reveal that the beam regular split is stable to the finite initial perturbations.  相似文献   

20.
In the real-world application of face recognition system, owing to the difficulties of collecting samples or storage space of systems, only one sample image per person is stored in the system, which is so-called one sample per person problem. Moreover, pose and illumination have impact on recognition performance. We propose a novel pose and illumination robust algorithm for face recognition with a single training image per person to solve the above limitations. Experimental results show that the proposed algorithm is an efficient and practical approach for face recognition.  相似文献   

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