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1.
在193 nm的单色激光实验中,本文利用时间切片离子速度成像技术,研究了经193 nm双光子电离得到的Si2+的解离反应动力学过程. 根据实验得到的Si+离子的速度成像,观测到了两种离子直接解离通道:Si(3Pg)+Si+(2Pu)和Si(1D2)+Si+(2Pu). 电子基态的Si2分子处于v=0∽5的振动态上,其经过双光子电离后激发到Si2+离子的多个电子激发态势能面,生成主要通道Si(3Pg)+Si+(2Pu),其中v=1的解离信号最强. 此外,由于势能曲线22Πg与32Πg相同对称性引起的避免性势能面交叉,生成次要反应通道Si(1D2)+Si+(2Pu). 通道Si(1D2)+Si+(2Pu)的产物亦可以由生成的基态Si2+(X4Σg-)吸收一个193 nm光子后解离得到,其对应产物则具有更大的动能.  相似文献   

2.
用电子密度泛函理论研究了N-质子化corrole(H4Cor+)和meso位芳基取代质子化corroles(H4TPC+、H4TpFPC+和H4TdCPC+)的几何构型、内消旋反应机理以及电子光谱. 结果表明,这些化合物均有两种稳定构型(势能面极小),一个为C2对称性的S1(最稳定构型),另一为C1对称性的S2,其中S1的能量比S2低约15.8~18.5 kJ/mol.S1和S2的corrole环都呈现明显的面外扭曲变形. 手性S1的两个对映异构体之间的转化是一个以S2为中间态的多步过程. 用TDDFT计算了它们的紫外可见电子吸收光谱和圆二色谱(ECD). 与H4Cor+相比,H4TPC+、H4TpFPC+和H4TdCPC+的紫外可见吸收都发生了明显红移,且它们的Q带都因芳基取代基与corrole环之间的π-π共轭而明显增强. 计算表明,质子化corrole的若干相邻电子跃迁的旋转强度符号相反,表明ECD谱可能是研究其电子跃迁的有用工具.  相似文献   

3.
通过密度泛函理论在气相条件下, 利用UB3LYP/6-311G(d)和HF/6-31G基组水平优化了过渡态的结构并寻找了能量最低点,发现酰胺氮和亚胺氧是最佳结合点,并分析了这些活性点的活化能大小以及≡Si+和≡SiO-基团和这些活性点的反应步骤,得出静电作用和离子配位效应是形成稳定复合物的主要因素,另外在形成稳定复合物过程中,亚胺氧转向作用和支链的大小和转向对降低整个复合物能量也起着重要的作用.  相似文献   

4.
利用脉冲激光溅射-超声分子束载带方法制备气相硼羰基络合物正离子. 采用红外光解离光谱研究了B(CO)3+、B(CO)4+ 和B2(CO)4+的振动光谱. 研究结果表明B(CO)3+具有非常强的B-CO键,无法直接获得其红外光解离光谱. 对B(CO)4+的光解离光谱研究表明该离子是一个B(CO)3+和CO之间弱相互作用络合物. 其中B(CO)3+核具有平面D3h对称性结构,中心硼具有稳定的8电子组态. B2(CO)4+具有平面的D2h对称性结构,其中的B-B键包含一个σ键和半个π键. 自然轨道能量分解分析(EDA-NOCV)表明在B(CO)3+和B2(CO)4+中的B-CO成键作用中OC→B(σ)要比B→CO(π)反馈作用强.  相似文献   

5.
用PBE1PBE方法研究了钒氧卟啉一价阴离子([VOP]-)、一价阳离子([VOP]+)的单态和三重态结构. 结果表明[VOP]-和[VOP]+的最稳定电子态均为三重态,其未配对电子一个占据钒的dxy轨道,另一个占据卟啉环的π轨道,因此两者均为π-自由基. 中性分子(VOP)的双重态最稳定,其未配对电子占据钒的dxy轨道. 双重态VOP具有较高的C4v对称性,而三重态[VOP]- 离子由于发生姜-泰勒效应对称性降低为C2v. 计算了[VOP]-姜-泰勒活性振动模式的电子-振动耦合常数,并用前线KS轨道的节面分布解释了姜-泰勒畸变沿特定简正模式发生的原因. 三重态[VOP]+ 阳离子的卟啉环发生键长交替变化,构型畸变起源于电子态近简并引起的赝姜-泰勒效应,导致其对称性从C4v降低为C4,其结构变化可以用重组的前线KS轨道的节面分布解释.  相似文献   

6.
本文通过离子迁移质谱法研究了氧化钠团簇阳离子(NanOm+n≤11)的稳定结构. 质谱结果表明化学计量组成Na(Na2O)(n-1)/2+ (n=3、5、7、9和11)系列是稳定的,并且NaO(Na2O)(n-1)/2+ (n=5、7、9和11)系列作为二级稳定系列. 为了获得这些团簇离子的结构,通过离子迁移率测量实验测定离子和氦缓冲气体之间的碰撞截面. 同时计算了这些组合物优化结构的理论碰撞截面. 结果表明,Na(Na2O)(n-1)/2+和NaO(Na2O)(n-1)/2+的结构除了n=9之外,其它具有相似结构框架. Na(Na2O)(n-1)/2+所有的化合键位于钠和氧之间. 另一方面,NaO(Na2O)(n-1)/2+中除了Na-O键之外,还存在一个O-O氧键,表明NaO(Na2O)(n-1)/2+具有过氧化物离子(O22-)作为Na(Na2O)(n-1)/2+的氧化物离子(O2-) 的替代物. Na(Na2O)(n-1)/2+和NaO(Na2O)(n-1)/2+两种稳定系列都是闭壳组合物. 这些闭壳特征对氧化钠簇阳离子的稳定性具有强烈影响.  相似文献   

7.
以Nb+与CS2反应作为第二前过渡金属离子与CS2反应生成金属硫化物离子和CS的范例体系. 采用密度泛函UB3LYP方法,对于Nb+采用Stuttgart赝势基组,对于C和S采用6-311+G(2d)基组,计算研究了Nb+在基态和激发态时与CS2气相反应的机理. 全参数优化了反应势能面上各驻点的几何构型,并且用频率分析方法和内禀反应坐标方法对过渡态进行了验证. 结果表明Nb+与CS2的反应是插入-消去反应,在反应过程中会发生系间窜越,并且找到了两个势能面的能量最低交叉点.  相似文献   

8.
本文使用文献中的N2H+(1-0)、H13CO+(1-0)、HCN(1-0)和HN13C(1-0)谱线数据研究大质量恒星形成团块的化学性质和演化,发现H13CO+和HN13C的丰度受H2柱密度的影响. 由于从A阶段到B阶段这两个丰度的中值增加了近10倍,H13CO+和HN13C适合追踪大质量恒星形成团块的演化. 从A到B阶段四种分子丰度增长速度从高到低依次为H13CO+、HCN、HN13C、N2H+. 结果表明进行光学薄分子谱线的高分辨率观测对于研究大质量恒星形成团块的化学演化是必要的.  相似文献   

9.
研究了含有低价族元素的反夹心化合物[E-C{5-n}H{5-n}Nn-E]+和[E-C{5-n}H{5-n}Pn-E]+(n=1,2,3; E=Al,Ga,In,Tl).(η5, η5) 配位的反夹心构型[E-C{5-n}H{5-n}Nn-E]+ 在能量上不稳定或不存在.而(η5,η5)配位的反夹心构型[E-C{5-n}H{5-n}Pn-E]+不但在能量上稳定, 在解离过程中也具有稳定性. 对于含有相同的E元素来说,[E-C{5-n}H{5-n}Pn-E]+的解离稳定性随着n的增加而降低;而对于确定的n来说, 含有不同E的化合物的解离能是类似的.其中[E-C4H4P-E]+的解离稳定性与已知的[E-C5H5-E]+非常相似.C{5-n}H{5-n}Pn与E之间的相互作用主要是离子性的. 由于在(η5,η5)配位的[E-C{5-n}H{5-n}Nn-E]+中,E和P原子上都具有孤对电子,因此该反夹心化合物可以作为多电子供体.  相似文献   

10.
一个化学反应的过程可能涉及多个绝热电子态,其中的非绝热耦合对反应机理起着重要的作用. 本文采用含时量子波包方法和轨线面跳跃方法研究了非绝热耦合对H+MgH+→Mg++H2反应的影响. 通过理论计算得到了绝热和非绝热近似下的反应态-态分辨的积分截面. 计算结果表明,当计算中忽略非绝热耦合时,反应遵循直接剥离的反应机理. 然而,当计算中包含非绝热耦合时,在反应过程中可以形成一个长寿命的激发态复合物(MgH2+)*,进而使反应遵循复合物形成反应机理. 通过轨线面跳跃计算,进一步揭示了直接剥离和复合物形成反应机理. 由非绝热耦合引起的复合物形成反应机理不仅提高了反应的活性,并且对产物的振动态分布具有显著影响.  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.
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   

14.
15.
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   

16.
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   

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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