Pre-resonance Raman studies of some mesogens-TB4A,TB7A and TB10A

Pre-resonance Raman spectra of certain liquid crystalline compounds, TB4A, TB7A and TB10A, are reported. The anomaly observed in the pre-resonance Raman spectra in the three compounds was initially explained by the Albrecht-Hutley Model, but its failure leads us to explain the anomalous intensity enhancement mechanism by invoking an interference effect between a weak dipole-forbidden excited state and a nearby strong electronic level via vibrational modes. The presence of a 2¹A_g dipole-forbidden excited state in TB4A and TB10A is deduced after an elaborate discussion of their centro-symmetric structure. The structural difference of TB7A in comparison with TB4A and TB10A is also discussed by taking their X-ray data into consideration.     

A comparative laser Raman study on TB4A, TB7A and TB10A

The basic structural differences between three thermotropic liquid crystals TB4A, TB7A and TB10A have been interpreted by analysing their Raman spectra. Three spectral regions, 925-1025, 1275-1475 and 1525-1650 cm-1, have been chosen in this context to incorporate their structural dissimilarity. The induced planarity of the backbone, as an effect of increasing chain length, has been studied by observing the changes in the respective Raman spectra of the three compounds. A tentative assignment of all the modes observed in the region 400-1700cm-1 is made in this context. The molecular conformations of the three compounds have been predicted in their solution states, and are compared with the molecular environment that exists in their liquid crystalline states. Structural disorder at the solid-SmG transition is discussed and the changes are incorporated systematically.     

Dynamics of a low temperature phase transition in liquid crystal TB10A probed by Raman spectroscopy

Raman spectra of TB10A were recorded in the regions, 925-1000 and 1140-1220cm-1 from room temperature down to 20 K, during cooling and heating cycles. The subtle changes in the spectral features of the bands at 975 and 1195cm-1 at 47 K were attributed to a hitherto unreported stable-metastable phase transition in TB10A. The dynamics of the new phase transition have been explained in terms of splitting of the non-planar mode at 975cm-1 owing to strong intermolecular interaction due to close molecular packing in the low temperature phase. The spectral anomaly of the 975cm-1 band, in terms of variation of relative intensity with respect to temperature, also shows the hysterisis linked with the process of stable-metastable-stable modification in TB10A.     

Dynamics of a low temperature phase transition in liquid crystal TB10A probed by Raman spectroscopy

Raman spectra of TB10A were recorded in the regions, 925-1000 and 1140-1220cm-1 from room temperature down to 20 K, during cooling and heating cycles. The subtle changes in the spectral features of the bands at 975 and 1195cm-1 at 47 K were attributed to a hitherto unreported stable-metastable phase transition in TB10A. The dynamics of the new phase transition have been explained in terms of splitting of the non-planar mode at 975cm-1 owing to strong intermolecular interaction due to close molecular packing in the low temperature phase. The spectral anomaly of the 975cm-1 band, in terms of variation of relative intensity with respect to temperature, also shows the hysterisis linked with the process of stable-metastable-stable modification in TB10A.     

A study of the B2 excited state geometries of the metal-metal quadruply bonded compounds Mo2X4(PMe3)4 (X = Cl, Br or I)

The excited state geometries of the metal-metal quadruply bonded compounds Mo₂X₄(PMe₃)₄ (X = Cl, Br or I) have been studied by means of resonance Raman and absorption spectroscopy. A fit of the parameters of a simple theoretical model to the experimental data indicates that the metal-metal bond increases some 10 pm on excitation to the ¹B₂ (δδ^*) state, whereas other geometric changes are small. Furthermore, the phenomenological lifetime factor of the excited state, Γ, is found to be dependent on the vibrational quantum number, ν, of this state.     

尿嘧啶和5-氯尿嘧啶1S0→1S2跃迁动态结构的共振拉曼光谱

采用含时量子波包理论的简单模型对5-氯尿嘧啶和尿嘧啶的共振拉曼光谱开展了强度分析拟合, 获得了1(π, π*)激发态的几何结构变化动态特征. 结果表明, 尿嘧啶1S0→1S2跃迁的动态结构特征因5-位氯原子取代而改变. 5-氯尿嘧啶的动态结构特征主要沿C5=C6伸缩振动+C6H12 弯曲振动和N3H9/N1H7弯曲振动+N1C6伸缩振动反应坐标展开, 而尿嘧啶的动态结构特征主要沿嘧啶环的伸缩振动+C5H11/C6H12/N1H7弯曲振动和C4=O10伸缩振动反应坐标展开. π和π*轨道中氯原子的pz电子参与嘧啶环的p-π共轭作用导致了在1(π, π*)激发态上5-氯尿嘧啶的振动重组能更多地配分给嘧啶环的弯曲振动模式和C5=C6伸缩振动模式. 尿嘧啶在甲醇中的激发态动态结构特征与在水中的基本一致, 但波包沿C5H11/C6H12/N1H7弯曲振动+N1C6伸缩振动(υ12)和环呼吸振动(υ17)反应坐标的运动明显增强.     

Excited-State Raman Spectroscopy of Inorganic Compounds

Abstract— Raman spectra of inorganic complexes in excited electronic states are discussed. A brief overview of the field of transient Raman spectroscopy and experimental considerations are presented. Two examples from the author's laboratory are used to illustrate the type of information that can be obtained. The first example, an excited-state Raman spectroscopic study of K₃[Mn(CN)₅NO], is chosen because it illustrates the connections between excited-state molecular structure and vibrational properties. The pump pulse causes a change from a linear sp-hybridized NO containing a triple bond to a bent sp²-hybridized NO containing a double bond. Both the NO stretch and normal modes involving other ligands are measured and interpreted. The second example is chosen to illustrate the vibrational consequences of photoinduced electron transfer. The Raman spectra of W(CO)₄(diimine) complexes (diimine = 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, and isopropyl-pyridine-2-carbaldehyde imine) in the lowest tungsten to diimine charge transfer excited state are discussed. The excited-state peaks are assigned to ligand ring deformation modes and to carbonyl stretching modes. The totally symmetric cis -carbonyl stretching mode in the charge transfer excited state is about 50 cm' higher in energy than that of the molecule in the ground electronic state. The increase is interpreted in terms of loss of metal-car-bonyl back-bonding in the charge transfer excited state. Finally, a summary of the field's strengths and difficulties and a brief discussion of the future perspectives are presented.     

Resonance Raman and density functional study of the excited state structural dynamics of 3-amino-2-cyclohexen-1-one in water and acetonitrile solvents

FT-Raman and/or FT-IR spectra of 3-amino-2-cyclohexen-1-one (ACyO) in solid state and/or in solvents of water and acetonitrile were obtained. Density functional theory calculations were done to help elucidate the vibrational band assignments. The A-band resonance Raman spectra of ACyO were acquired in water and acetonitrile solvents to examine the excited state structural dynamics and the state-mixing or curve-crossing tuned by solvents. A preliminary resonance Raman intensity analysis using the time-dependent wave-packet theory and simple model was done for ACyO in acetonitrile solvent. Resonance Raman spectroscopic probing of the excited state curve-crossing or state-mixing was proposed.     

1,2,3,4-四氢喹啉-4-酮衍生物的线性及非线性光学性质

合成了一系列具有刚性结构的推拉型1,2,3,4-四氢喹啉-4-酮衍生物: 1-苄基-1,2,3,4-四氢喹啉-4-酮(BTHQ)、2-(1,2,3,4-四氢喹啉-4-叶立德)丙二腈(THQM)、1,6-二羰基久洛尼定(DOJ)和1,6-二(二氰甲烯基叶立德)久洛尼定(BDCJ).测定了其吸收光谱、单光子荧光光谱和双光子上转换荧光光谱. 这类化合物的单双光子荧光参数都存在着很强的、规则的溶剂效应, 表明分子激发态可能存在较大的极性. 它们的二氯甲烷溶液在800 nm飞秒激光(150 fs)照射下, 能够发射出很强的双光子上转换荧光. 采用非线性透过率法测得四个化合物的双光子吸收截面在0.83～23.95×10－50 cm4•s•photon－1之间. 这类化合物的激发态存在有效的分子内电荷转移, 对双光子吸收和双光子荧光发射有较大贡献.     

Spectroscopic consequences of a mixed valence excited state: quantitative treatment of a dihydrazine diradical dication

A model for the quantitative treatment of molecular systems possessing mixed valence excited states is introduced and used to explain observed spectroscopic consequences. The specific example studied in this paper is 1,4-bis(2-tert-butyl-2,3-diazabicyclo[2.2.2]oct-3-yl)-2,3,5,6-tetramethylbenzene-1,4-diyl dication. The lowest energy excited state of this molecule arises from a transition from the ground state where one positive charge is associated with each of the hydrazine units, to an excited state where both charges are associated with one of the hydrazine units, that is, a Hy-to-Hy charge transfer. The resulting excited state is a Class II mixed valence molecule. The electronic emission and absorption spectra, and resonance Raman spectra, of this molecule are reported. The lowest energy absorption band is asymmetric with a weak low-energy shoulder and an intense higher energy peak. Emission is observed at low temperature. The details of the absorption and emission spectra are calculated for the coupled surfaces by using the time-dependent theory of spectroscopy. The calculations are carried out in the diabatic basis, but the nuclear kinetic energy is explicitly included and the calculations are exact quantum calculations of the model Hamiltonian. Because the transition involves the transfer of an electron from the hydrazine on one side of the molecule to the hydrazine on the other side and vice versa, the two transitions are antiparallel and the transition dipole moments have opposite signs. Upon transformation to the adiabatic basis, the dipole moment for the transition to the highest energy adiabatic surface is nonzero, but that for the transition to the lowest surface changes sign at the origin. The energy separation between the two components of the absorption spectrum is twice the coupling between the diabatic basis states. The bandwidths of the electronic spectra are caused by progressions in totally symmetric modes as well as progressions in the modes along the coupled coordinate. The totally symmetric modes are modeled as displaced harmonic oscillators; the frequencies and displacements are determined from resonance Raman spectra. The absorption, emission, and Raman spectra are fit simultaneously with one parameter set. The coupling in the excited electronic state H(ab)(ex) is 2000 cm(-1). Excited-state mixed valence is expected to be an important contributor to the electronic spectra of many organic and inorganic compounds. The energy separations and relative intensities enable the excited-state properties to be calculated as shown in this paper, and the spectra provide new information for probing and understanding coupling in mixed valence systems.     

2,4-二硫代尿嘧啶的紫外吸收光谱和共振拉曼光谱

硫代嘧啶碱基是光动力疗法潜在的重要光敏剂,其最低单重激发态的光物理研究已有广泛报道。然而,其较高激发态的跃迁性质和反应动力学研究较为稀少。因此,本文采用共振拉曼光谱和密度泛函理论计算方法研究2,4-二硫代尿嘧啶的紫外光谱和几个较高单重激发态的短时结构动力学。首先,基于共振拉曼光谱强度与电子吸收带振子强度f的关系,将紫外光谱去卷积成四个吸收带,分别为358 nm(f=0.0336)中等强度吸收带(A带),338 nm(f=0.1491)、301 nm(f=0.1795)和278 nm(f=0.3532)强而宽的吸收带(B、C和D带)。这一结果既吻合密度泛函理论计算结果,又符合共振拉曼光谱强度模式对紫外光谱带的预期。据此,去卷积得到的四个吸收带被分别指认为S0→S2跃迁、S0→S6跃迁、S0→S7跃迁和S_0→S_8跃迁。同时,分别对B,C和D带共振拉曼光谱进行了详细的指认,获得了短时动力学信息。结果表明,S_8态短时动力学的显著特征是在Franck-Condon区域或附近发生了S8(ππ~*)/S(nπ~*)势能面交叉引发的、伴随超快结构扭转的非绝热过程。S7和S6态短时动力学的主要特征是反应坐标的多维性,它们分别沿C_5C_6/C_2S_8/C_4S_(10)/N_2C_3+C_4N_3H_9/N_1C_2N_3/C_2N_1C_6/C_6N_1H_7/C_5C_6H_(12)和C_5C_6/N_3C_2/C_4S_(10)/C_2S_8+C_6N_1H_7/C_5C_6H_(12)/C_5C_6N_1/C_5C_6H_(12)/C_2N_1C_6/N_1C_2N_3/C_4N_3H_9/N_1C_2N_3等内坐标演化。     

Polarized Raman Spectra VIII. Ramam Intensities of Anthracene Excited by Different Laser Light

An Ar-Kr ion laser was used to excite the Raman spectrum of powdered anthracene with two laser lines of 4880 and 6471 Å. There are significant differences in the intensity distribution in these two Raman spectra. These differences can be best explained by considering that Raman intensities are contributed by two allowed excited states of anthracene, and their contributions depend upon the laser frequency. From these Raman spectra, it is also possible to infer the vibrational structures in the higher energy, structureless excited state of anthracene.     

Ab initio calculation of resonance Raman cross sections based on excited state geometry optimization

A method for the calculation of resonance Raman cross sections is presented on the basis of calculation of structural differences between optimized ground and excited state geometries using density functional theory. A vibrational frequency calculation of the molecule is employed to obtain normal coordinate displacements for the modes of vibration. The excited state displacement relative to the ground state can be calculated in the normal coordinate basis by means of a linear transformation from a Cartesian basis to a normal coordinate one. The displacements in normal coordinates are then scaled by root-mean-square displacement of zero point motion to calculate dimensionless displacements for use in the two-time-correlator formalism for the calculation of resonance Raman spectra at an arbitrary temperature. The method is valid for Franck-Condon active modes within the harmonic approximation. The method was validated by calculation of resonance Raman cross sections and absorption spectra for chlorine dioxide, nitrate ion, trans-stilbene, 1,3,5-cycloheptatriene, and the aromatic amino acids. This method permits significant gains in the efficiency of calculating resonance Raman cross sections from first principles and, consequently, permits extension to large systems (>50 atoms).     

Single-site absorption spectroscopy of pheophytin-a and chlorophyll-a in a n-octane matrix

Site-selection experiments have been performed on pheophytin-a and chlorophyll-a in n-octane at 4.2 K. Single-site absorption spectra of both compounds were recorded, but single-site emission spectra could not be obtained. The absorption spectra show sharp lines and vibrational frequencies of the lowest excited singlet state correspond with resonance Raman frequencies. A remarkable feature of the emission is the presence of a strong 0-0 transition but extremely weak vibronic transitions.     

Resonance Raman Spectroscopy,and Its Application to Inorganic Chemistry. New Analytical Methods (27)

Resonance Raman spectra are obtained when the wave number of the exciting radiation is close to, or coincident with, that of an electronic transition of the scattering species. Such spectra are usually characterized by a very large enhancement of the intensities of particular Raman bands, sometimes with the appearance of intense overtone and combination tone progressions. The technique provides detailed information about excited electronic states because it is only the vibrational modes associated with the chromophore that are resonance-Raman active. Additionally, the high sensitivity is such that compounds at concentrations as low as 10^?6 mol/L may be detected, enabling resonance Raman spectroscopy to be used as an analytical tool and for the study of chromophores in molecules of biological interest.     

Theoretical investigation of the weak interactions of rare gas atoms with silver clusters by resonance Raman spectroscopy modeling

The interactions of rare gas atoms (Rg = Ar, Kr, and Xe) with small neutral and cationic silver clusters have been investigated by density functional methods and the effect of these weak interactions on the resonance Raman spectra of the complexes has been evaluated. The resonance Raman technique that depends on the properties of ground and excited state, seems deeply sensitive to the weak rare gas–metal cluster interactions, and the use of inert gases has been proven to be an excellent approach to recognize the ability of this technique to detect extremely weak interactions. In this work, for , and complexes the IR, normal and resonance Raman spectra have been calculated and the effect of rare gas–cluster stretching vibration ( ) on the pattern and the relative intensities of different spectra have been investigated. The resonance Raman spectra for the weakly interacted complexes (with the interaction energies less than ?2.0 kcal/mol) exhibit the vibration with the detectable intensity that its intensity increases by going from Ag₆–Ar to Ag₆–Xe complex. Moreover, the resonance Raman spectra (based on the excited state gradient approximation) for high intensity nearly degenerate excited states, proved the effect of accumulation of the excited state charge density on the relative intensity of vibration.     

Interpretation of resonance cars and shpolskii spectra with calculated molecular geometries,vibrational frequencies and relative intensities: Chrysene in it's lowest excited singlet and triplet state

Coherent anti-Stokes Raman scattering (CARS) spectra of excited molecules as well as Shpolskii spectra provide information about geometry changes between ground and excited states. Vibrational frequencies and relative intensities from recently obtained CARS spectra of the chrysene S₁ and T₁ state and earlier observed Shpolskii spectra are interpreted in terms of molecular geometry and force-field changes by means of quantum-chemical consistent force field (QCFF) and Franck-Condon factor calculations. The comparison of observed and calculated relative intensities indicates a coupling between the S₁ and S₂ state enhancing some of the vibrational radiative singlet transitions both in absorption and fluorescence spectra whereas within the phosphorescence spectra proportionality to calculated Franck-Condon factors is obeyed. The T₁ state is the more loosely bound state and its geometry change is different from that of the S₁ state. The resonance CARS transitions in the S₁ state are assigned to totally symmetric vibrations getting their intensity by a coupling scheme analogous to the A term of the resonance Raman effect: the relative intensity of a transition is shown to be proportional to the Franck-Condon factor to the higher excited state and to the squared vibrational frequency. Using this relation this state can be identified by means of its finger-print-like intensity pattern.     

Ground and excited states calculations of 7-phenylamino-substituted coumarins

A theoretical calculation of the ground and first excited states of two 7-phenylamino-substituted coumarin compounds are performed. In order to study the effect of phenyl substituted in amino group and fluorine atoms substituted in methyl group, 7-amino-4-methyl coumarin (C120) and 7-amino-4-(trifluoromethyl) coumarin (C151) were also studied. The geometries of the ground state and the first ground state were optimized using density function theory and configuration interaction singles levels of theory. Molecular orbitals (MO) of the ground and first excited states of the four coumarin compounds were obtained to explain the change of the structures. ZINDO and TD-DFT methods with different basis sets were applied to predict the UV absorption spectra. The solvent effect had also been taken into account using self-consistent isodensity polarized continuum model. The predicted spectra are in agreement with the experimental data.     

Multiplex binding modes of toluidine blue with calf thymus DNA and conformational transition of DNA revealed by spectroscopic studies

It is noteworthy to understand the details of interactions between antitumor drugs and DNA because the binding modes and affinities affect their antitumor activities. Here, The interaction of toluidine blue (TB), a potential antitumor drug for photodynamic therapy of tumor, with calf thymus DNA (ctDNA) was explored by UV–vis, fluorescence, circular dichroism (CD) spectroscopy, UV-melting method and surface-enhance Raman spectroscopy (SERS). The experimental results suggest that TB could bind to ctDNA via both electrostatic interaction and partial intercalation. The fluorescence quenching of TB by ctDNA was static and due to electron transfer from bases to the excited singlet state of TB. At low [TB]/[DNA] ratio, TB mainly partially intercalated into ctDNA resulting in the slight increase of base stacking degree; at high [TB]/[DNA] ratio, excessive TB externally stacked along the helix surface via coupling with partially intercalated ones, thereby inducing B-A transition of ctDNA. The conformational transition of DNA was confirmed by the obvious improvement of the thermal stability of ctDNA. The SERS spectra suggest that TB could partially intercalate into DNA basepairs with its ring C₁NC_1′ side buried.     

Raman spectroscopy from a picosecond-lived excited state of methyl orange

Vibrational Raman scattering from a picosecond-lived excited state of methyl orange in 9 N H₂SO₄ is reported. The vibrational frequencies of normal modes in ground and electronic excited states are separated by ≈ 10 cm^?1 but rather large differences exist in their intensities. In particular, the intensity of a mode at ≈ 1180 cm^?1, due to the NN stretch, is sensitive to the frequency of the nanosecond pulsed tunable laser. A bandwidth comparison between ground- and excited-state spectra reveals that the widths of bands of the latter, like that of the former are due to dephasing and other effects associated with interaction of molecules in the liquid phase.