有机化合物电子光谱中的助色基及其作用机理探讨(Ⅰ)

本文就电子光谱中助色基的作用进行了讨论 ,认为不能一概地认为助色基能使与之相连的生色基最大吸收波长统统发生红移 ,而应具体问题具体分析 :对于n→π 来说 ,一方面助色基的p轨道和生色基的最低π 反键空轨道相互作用 ,使π 反键轨道能量上升 ,另一方面助色基的p轨道和生色基的n轨道正交 ,n轨道能量基本保持不变 ,因此n→π 跃迁能增加 ,吸收波长发生蓝移。对于π→π 跃迁来说 ,助色基的p轨道和生色基的最高π成键轨道相互作用生成的新的最高π成键轨道 ,能量虽然有所升高 ,但升高的程度与π 反键轨道升高的程度相比 ,在一些化合物中π轨道升高程度较大 ,因而π→π 跃迁能减小 ,吸收波长发生红移 ;在另一些化合物中π轨道升高程度较小 ,因而π→π 跃迁能增加 ,吸收波长发生蓝移。     

C42〈Al〉C32〈Si〉等混合物吸收光谱特性

用电弧放电＾［１］、Ｈｅ气对流的方法制备出了含Ｃ４２〈Ａｌ〉、Ｃ３２〈Ｓｉ〉、Ｃ２８〈Ｆｅ〉和Ｃ３０〈Ｃａ〉的混合物。对该混合物作了吸收光谱测量，并与Ｃ６０等全碳分子的吸收光谱作了比较，结果表明，Ａｌ、Ｓｉ、Ｃａ和Ｆｅ原子嵌入Ｃ４２等全碳分子后，并没改变吸收峰位，而只是改变了分子的π→π＾＊跃迁和ｎ→π＾＊跃迁几率。     

β-三苯锗基丙酸及β-三苯锗基丁酸的拉曼及红外光谱

我们合成了有机锗化合物的一类重要中间体β-三苯锗基丙酸和β-三苯锗基丁酸 ,测量了该化合物的拉曼光谱和红外光谱 ,经光谱分析 ,指认了主要波数所对应的分子振动。在这两种化合物的拉曼光谱中 ,30 50 cm- 1( m)、1 0 2 5cm- 1( m)和 61 8cm- 1( m)分属于 Ph- H的伸缩振动、面内弯曲振动和面外扭曲振动。饱和 Ge- C键的振动分别在 594cm- 1和 587cm- 1,同时指出了 Ph- Ge的几种振动所对应的振动频率。在红外光谱中 ,C=O的振动出现在 1 70 9cm- 1( s)和 1 70 5cm- 1( s) ,与饱和碳相连接的 Ge- C振动出现在 61 7cm- 1( w)和 61 7cm- 1( w)。     

锰、铁、钴氮杂金属冠醚的红外和紫外光谱研究

本文报导了含铁、钴、锰氮杂金属冠醚及其配体的红外和紫外光谱研究结果。对400－4000cm^-1范围的主要红外吸收谱峰进行了经验归属，并进一步讨论了合成的配体和配合物的特征吸收谱带与其结构的关系。配体IR谱中的v(C=O),v(NH),δ（NH） v(CN),δ（NH）等酮式特征吸收在配合物的IR谱图中基本消失，－1600cm^-1处出现归属于共轭体系C＝N－N＝C骨架伸缩振动的吸收谱带，－1560和－1410cm^-1附近各出现一尖锐的强吸收，他们分别归属于v(C=O)和v(CO)，说明该系列N－烷酰基水杨酰肼配体固态时主要以酮式存在，在溶液中则先异构为烯醇式结构，然后醇羟基再通过去质子化作用使羟氧与金属配合。电子光谱研究结果表明该系列配合物出现苯环及共轭体系的π-π^*或n-π^*的跃迁（－204和220－256nm)、M－L荷移跃迁带（274－350nm)和在配位体场作用下金属原子的d-d跃迁吸收峰（－500nm)。     

Line Positions and Intensities in the 2nu(2)/nu(4) Vibrational System of (14)NH(3) near 5-7 µm

Line positions and intensities belonging to the vibrational system 2nu(2)/nu(4) of ammonia (14)NH(3) are measured and analyzed between 1200 and 2200 cm(-1) in order to improve the molecular database. For this, laboratory spectra are obtained at 0.006 and 0.011 cm(-1) unapodized resolution and with 4% precisions for the intensities using Fourier transform spectrometers located at the Kitt Peak National Observatory and the Jet Propulsion Laboratory. The observed data contain transitions of the nu(4) fundamental band near 1626.276(1) and 1627.375(2) cm(-1) (for s and a inversion upper states, respectively) and the 2nu(2) overtone band near 1597.470(3) and 1882.179(5) cm(-1) (for s and a inversion states, respectively). A total of 2345 lines with J' 相似文献   

Near-Infrared Laser Spectroscopy of TiS: The b(1)Pi-X(3)Delta Transition

Laser-induced fluorescence spectrum of TiS in the 769-863 nm region has been recorded and analyzed. The TiS molecule was produced using the technique of laser vaporization/reaction with supersonic cooling. Twenty-one weak subbands have been assigned as being due to b(1)Pi-X(3)Delta, B(3)Pi(0)-X(3)Delta(1), and C(3)Delta-X(3)Delta transitions. Strong evidence shows that the b(1)Pi state is responsible for perturbing the v = 0, 1, and 2 levels of the C(3)Delta(1) subband. The molecular constants of the b(1)Pi state have been determined as follows: T(e) = 10 589.47 cm(-1), omega(e) = 542.14 cm(-1), omega(e)x(e) = 3.16 cm(-1), B(e) = 0.19568 cm(-1), and alpha(e) = 0.00085 cm(-1). The spin-orbit interaction between the b(1)Pi (v = 2 and 3) and C(3)Delta (v = 1 and 2) levels is discussed in terms of configuration interaction occurring between the b(1)Pi from the 11varsigma(1) 5pi(1) configuration and the (1)Pi from the 5pi(1) 1delta(1) configuration, and the C(3)Delta state from 12varsigma(1) 1delta(1) configuration. Copyright 2000 Academic Press.     

Dynamic stabilization in 1sigma(u)-->1pi(g) excited nitrogen clusters

High-resolution 1s near-edge spectra of molecular nitrogen and variable size nitrogen clusters obtained using monochromatic synchrotron radiation from the high brilliance BESSY-II storage ring facility are reported. The vibrationally resolved 1sigma(u)-->1pi(g) core-to-valence excitation band of clusters shows a distinct redshift of 6+/-1 meV relative to the isolated molecule, but the vibrational structure and linewidths are essentially unchanged. This shift is assigned to dynamic stabilization of 1sigma(u)-->1pi(g) excited molecules in clusters, arising from the dynamic dipole moment generated by core-hole localization in the low-symmetry cluster field. This leads to changes in intermolecular interactions compared to the ground-state cluster. Such spectral shifts are expected to occur generally in molecular clusters and in the corresponding condensed phase.     

一价镧离子高n里德伯态

基于五步激光共振激发,经由中间态(Xe) 5d6d~3F_2的一价镧离子光谱,分析了该实验谱,确定了一价镧离子一强一弱两个自电离里德伯系列.同时利用多通道量子亏损理论(MQDT)框架下的相对论多通道理论(RMCT)计算,标识了这两个自电离里德伯系列,强的自电离里德伯系列标识为5dnp(5/2,1/2)_3和/或5dnp(5/2,1/2)_2,弱系列标识为为5dnf(5/2,5/2)_3和/或5dnf(5/2,5/2)_2.根据实验谱峰数据,发现有效量子数很高时,里德伯和自电离里德伯能级量子数亏损随激发能量不平滑变化,并分析了可能的原因.     

Probing antiaromaticity: resonance Raman investigation of a series of differently substituted boroles

We report an investigation of four differently substituted boroles by resonance Raman (RR) spectroscopy with the aim of gaining insight into the structural changes that occur upon electronic π–π* excitation in the five‐membered BC₄ ring. Such boroles are prototypes for the theory of antiaromaticity, because the empty p_z orbital at the boron interacts with the π system of the carbon backbone to delocalize the four π electrons. The magnitude of this interaction depends on the substituents at the boron atom. In all compounds, an intense band appears around 1600 cm⁻¹, which can be assigned to a CC stretching vibration. The selective amplification of this mode indicates an expansion of the borole ring upon electronic excitation. The resonant enhancement of another mode at around 1300 cm⁻¹, which can be assigned to a vibration between the boron and the substituent, gives evidence that the degree of antiaromaticity in the borole depends strongly on the interaction between the substituent at the boron atom with the empty p_z orbital of the boron. When the boron is connected to a ferrocene, this band appears with high intensity, indicating a strong interaction between B and Fe. Furthermore, we studied the dependence of the excitation wavelength on the Raman intensities. In addition, we used DFT calculations to determine the vibrational wavenumbers. Copyright © 2009 John Wiley & Sons, Ltd.     

Satellite band in the rovibrational spectrum of CO2 in helium droplets

Pulsed infrared (nu approximately 2350 cm(-1)) laser excitation spectra of CO2 molecules embedded in helium droplets are reported. The spectra exhibit a sharp R(0) rovibrational line accompanied by a weak broader (deltanu approximately 10 cm(-1)) satellite band, which is shifted by 14 cm(-1) towards higher frequencies. We assign this satellite band to a simultaneous rovibrational excitation of a molecule and its helium solvation shell. The results are rationalized within a model, which includes coupling of the rotational states of a molecule and a ring of He atoms.     

有机化合物电子光谱中的助色基及其作用机理探讨(Ⅱ)

助色基的未成键电子对与生色基的最低π~*反键轨道和最高π成键轨道线性组合成三个新的分子轨道。其中能量最高的π~*是反键轨道,它的能量一定高于原生色基的π~*轨道;最高占据π轨道的能级与原生色基的π轨道相比,孰高孰低将随生色基和助色基的不同而异;原生色基的n轨道与助色基的未共用电子对所占轨道相互正交,故两者间的作用可忽略不计,n轨道能级基本保持不变。因此助色基使生色基的n→π~*跃迁吸收波长发生蓝移,而π→π~*跃迁吸收波长是红移还是蓝移,则随生色基及助色基的不同而异。     

High-resolution rotational spectroscopy in a cold ion trap: H2D+ and D2H+

The lowest-lying 1(01) <-- 0(00) transition of para-H(2)D(+) and 1(11) <-- 0(00) of ortho-D(2)H(+) has been detected by the enhancement of the D/H isotope exchange reaction in collisions with p-H2 upon rotational excitation. These are the first pure rotational spectra of molecular ions by action spectroscopy. For this purpose, a cryogenic multipole ion trap has been combined with narrow-band tunable radiation sources operating in the 1.25 to 1.53 THz range. The low temperature of the ions allows us to determine the astronomically important transitions with a relative precision of Delta nu/nu=10(-8). While the 1 476 605.708(15) MHz line center frequency for the o-D(2)H(+) transition agrees very well with previous unpublished work, the 1 370 084.880(20) MHz line center frequency for the p-H(2)D(+) transition deviates by 61 MHz. Potential future applications of this new approach to rotational spectroscopy are discussed.     

Tm:YVO4晶体的光谱参数计算

由测量的Tm :YVO4晶体的吸收光谱 ,考虑到单轴晶体在各个方向上的吸收不同和折射率随波长的变化 ,根据Judd Ofelt理论计算了Tm3 +在YVO4中的强度参数、各个能级的振子强度、自发辐射几率、荧光分支比、积分发射截面等参数。强度参数为Ω2 =1 9416× 10 - 2 0 (cm2 ) ,Ω4=0 15 6 8× 10 - 2 0 (cm2 ) ,Ω6=0 396 3× 10 - 2 0 (cm2 )。计算结果表明 ,1 D2 → 3 F4的跃迁几率远大于1 D2 向其他各个能级的跃迁几率     

High-Resolution Laser Spectroscopy of YbCl: The A(2)Pi-X(2)Sigma(+) Transition

The A(2)Pi-X(2)Sigma(+) transition of (174)Yb(35)Cl and (172)Yb(35)Cl has been rotationally analyzed for the first time. Doppler-limited laser excitation spectroscopy with selective detection of fluorescence was used to obtain spectra of the 0-0 and 1-0 bands with a measurement accuracy of approximately 0.0035 cm(-1). Resolved fluorescence was used to record the 0-1, 0-2, and 0-3 bands and to unequivocally assign the rotational numbering, N, to the laser excitation spectra. In total, over 1300 line positions have been measured and assigned for each of the two isotopomers and employed in least-squares fits of molecular parameters. The principal results for the A(2)Pi state are A(e) = 1491.494(2) cm(-1) and R(e) = 2.4433(1) ?, and for the X(2)Sigma(+) state, R(e) = 2.4883(2) ? and gamma(e) = 4.59(2) x 10(-3) cm(-1). The interaction between the X(2)Sigma(+) and A(2)Pi states has been investigated and is shown to be the main contributor to the spin-rotation splitting in the ground state. Copyright 2000 Academic Press.     

Spectral signs of the internal heavy-atom effect in aliphatic carbonyl compounds

The CNDO/S method has been applied to the internal effect of Si on the electronic spectrum of the acetone molecule; there is a considerable bathochromic shift and an increase in the \(S_0 \to S_{n\pi ^ * } \) intensity for theα-silyl ketones, while theβ-silyl ketons give only an increase in the intensity of \(S_0 \to S_{n\pi ^ * } \) absorption relative to acetone. The heavy atom substantially alters \(f_{S_0 \to T_{n\sigma ^* } } \) and \(\tau _{T_{n\sigma ^* } }^0 \) but has little effect on \(f_{S_0 \to T_{n\pi ^* } } \) and \(\tau _{T_{n\pi ^* } }^0 \) .     

High-Resolution Laser Photoacoustic Spectroscopy of HSiF(3): The 5nu(1) and 6nu(1) Overtone Bands

A spectrum of HSiF(3) has been recorded at room temperature with a gas pressure of 20-50 Torr in the near-infrared region. A laser photoacoustic spectrometer consisting of a longitudinal resonant cell coupled to a titanium:sapphire ring laser was employed. The 5nu(1) and 6nu(1) overtone bands of H(28)SiF(3) associated with the Si-H stretching have been observed at high resolution (3 x 10(-2) cm(-1)) in the regions 10 900-10 960 and 12 875-12 925 cm(-1), respectively. About 450 lines of the 5nu(1)-0 band have been assigned (J 相似文献   

Theory of nonlinear Sagnac effect

A nonlinear wave interaction is considered as a technique to increase the rotation sensitivity of the ring laser. The gyroscopic scale factor K is calculated in an active laser gyro with a dispersive medium. K is in reverse proportion to the group index n* = n + vdn/dv of the medium. In a monolithically-integrated GaAs ring laser, the value K ∼5000 is obtainable (radius ∼1 cm) in a linear case. In the presence of a strong wave, the dynamic nonlinear anomalous dispersion can provide an increase of K by 10–100 times in the vicinity of critical points where n* passes zero. An expression of K is derived for the nonlinear Sagnac effect. The nonlinear dispersion is discussed in terms of “slow/fast” light.     

NO2分子在440～495 nm范围内的激光诱导荧光激发谱

以 NdYAG脉冲激光器泵浦的光学参量发生器/放大器作激发光源, 获得了室温、低气压条件下, NO2分子在440～495 nm波长范围内的激光诱导荧光激发谱, 将所得谱线峰归属为NO2由基电子态X2A1态向第二电子激发态B2B1态的跃迁, 利用实验所得峰值波长计算了NO2分子B2B1态的角振动频率ωe. 通过对NO2分子B2B1→X2A1跃迁的荧光时间分辨光谱进行实验研究, 得到15 Pa气压下B2B1(0, 9, 0)振动态的能级寿命τ=49 μs. 测量了荧光寿命随气压的变化关系, 利用曲线拟合得到NO2 B2B1(0, 9, 0)振动态的自发辐射寿命τ0≈55 μs和无辐射跃迁弛豫速率常数. kq=1.2×10-9 cm3 molecule-1s-1.     

Investigation of Hadronic Quasi-Three-Body B Decays

We interest to investigate of the quasi-three-body decays of B⁰ meson to \({f_0}(980){K^ + }{\pi ^ - }({f_0}(980) \to \pi \pi )\) and \({\bar D_1}{(2420)^0}{\pi ^ + }{\pi ^ - }(\bar D_1^0) \to D{^{*-} }{\pi ^ + }\). The analysis of mentioned four-body decays is such as to factorize into the three-body decay and several channels observed. Hadronic three-body decays include both non-resonant and resonant contributions, on the basis of the factorization approach. In the case of B⁰ to vector pseudoscalar states appeared in factorized terms, the B* pole contribution is considered. Hence the matrix element of the B* → D₁ weak transition and strong vertex is computed. Therefore the theoretical values are (1.418 ± 0.21) × 10^?6 and (1.44 ± 0.2) × 10^?4, while the experimental results of them are \((1.4_{-0.6}^{+0.5})\times10^{-6}\), respectively. Comparing computational analysis values with experimental values show that our results are in agreement with them.     

α-呋喃酯的结构与红外光谱特征

总结和归属了α－呋喃甲酸酯α－呋喃甲醇酯和α－呋喃丙烯酸酯的主要红外吸收谱带和特征,讨论了其红外吸收频率随取代基结构而变化的规律。结果表明：α－呋喃环存在三个明显的吸收特征,α－呋喃丙烯酸酯中ＶＣ＝Ｃ约为１６４１ｃｍ＾－１,δ＝Ｃ－Ｈ面外变角振动频率为９７３ｃｍ＾－１,表明双键为反式构型。ＶＣ＝Ｏ约为１７１３ｃｍ＾－１,Ｃ－Ｏ－Ｃ键对称与伸缩振动在１３０５,１２６２和１１６５ｃｍ＾－１处产生三个强