Analysis of the two-photon absorption spectrum of benzonitrile based on the direct quantum-mechanical calculation of the intensity distribution

A direct quantum-mechanical calculation of the intensity distribution in the two-photon absorption spectrum of benzonitrile is performed taking into account the Herzberg-Teller effect. The excitation mechanism of all the observed lines, including lines corresponding to the excitation of single-quantum nontotally symmetric vibrations and their combinations with totally symmetric modes, is analyzed. The results of the calculation, performed taking into account the frequency effect and the Duschinsky effect, agree satisfactorily with experimental data. This indicates that it is worthwhile to apply the quantum-mechanical method in calculations of the intensity distribution in the two-photon absorption spectra of cyclic molecules.     

Quantum-mechanical calculation of the intensity distribution in resonance Raman spectra of guanine-cytosine pair

The method of quantum-mechanical calculation of the relative line intensities in the resonance Raman (RR) spectra of polyatomic molecules, which was previously applied to the analysis of the spectra of individual cyclic molecules and makes it possible to take into account the Herzberg-Teller and Duschinsky effects, as well as the frequency effect, is applied for the first time to the calculation of the spectra of a pair guanine-cytosine. Satisfactory agreement between the calculated results and the available experimental data is obtained. The particular features of the intensity distribution in the RR spectra of the guanine-cytosine pair excited by laser radiation at 266, 240, 218, and 200 nm are analyzed. The RR spectra of the guanine-cytosine pair are compared with the spectra of the individual guanine and cytosine molecules excited by the laser radiation at the same wavelengths.     

The Dushinsky effect and sum rules for vibronic transitions in polyatomic molecules

A method is presented for analyzing, in terms of sum rules, the intensity distribution among the vibronic bands in electronic spectra of polyatomic molecules, taking into account the rotation of the excited-state normal coordinates relative to those of the ground state (the Dushinsky effect). In the harmonic oscillator approximation, a quantitative criterion for the occurrence of the Dushinsky effect is obtained. The existence of this effect leads to non-product formulas for probabilities of the joint excitation of different vibrational modes. Expressions are obtained for the mean number of quanta excited in a given mode, and for its standard deviation, as well as for the correlation coefficients. The proposed method does not require a complete vibrational analysis of the spectrum of interest. As an example, the calculation of the correlation coefficient for the 3700-Å band system of the absorption spectrum of SO₂ is given.     

Application of quantum mechanical method to analysis of the intensity distribution in spectra of resonant hyper-Raman scattering of low-symmetry molecules

The quantum-mechanical method of calculating the relative intensities of lines in the spectra of resonant hyper-Raman scattering of polyatomic molecules in the Herzberg-Teller approximation is tested with respect to low-symmetry molecules. The method makes it possible to describe resonant Raman and hyper-Raman scattering spectra, as well as vibronic absorption spectra, from the same viewpoint based on a common set of parameters. The particular features of the implementation of the method are discussed based on the calculation of the spectra of resonant hyper-Raman scattering of chlorobenzene and adenine, and the expedience of the application of the method is illustrated. Satisfactory agreement is obtained between calculation results and available experimental data.     

Sequential spectral lines and intensity distribution in electronic-vibrational bands of free polyatomic molecules

The intensity distribution, the spectral band profile, and the temperature dependences of spectral characteristics of bands in the electronic-vibrational (vibronic) spectra of free polyatomic molecules are studied based on the concept of sequential lines (SLs) as constituent elements of these bands. It is shown that the intensity distribution in a separate electronic-vibrational band is defined by the convolution of an SL profile with the frequency distribution function of sequential transitions. Expressions for the intensity distribution in homogeneously and inhomogeneously broadened electronic-vibrational bands are derived, and specific features of their spectral behavior are determined. Using the latter results, distinguishing features or criteria of the character of broadening of the vibronic spectra of free polyatomic molecules are formulated.     

Quantum-mechanical calculation of the intensity distribution in the resonance Raman spectrum of benzonitrile

A direct quantum-mechanical calculation of the resonance Raman spectrum of a benzonitrile molecule upon excitation with laser radiation at a wavelength of 228.7 nm is performed in the Herzberg-Teller approximation with allowance made for the Duschinsky effect. The results of the calculation are in reasonable agreement with the available experimental data. The intensity distribution in the calculated resonance Raman spectrum of the benzonitrile molecule is compared with the intensity distributions in the spectra of benzene, methyl-substituted benzenes, and halogenated benzenes. It is revealed that the intensity distributions in the resonance Raman spectra of these compounds are characterized by a number of common features.     

Modeling of the time-resolved vibronic spectra of polyatomic molecules: The formulation of the problem and analysis of kinetic equations

A semiempirical parametric method is proposed for modeling three-dimensional (time-resolved) vibronic spectra of polyatomic molecules. The method is based on the use of the fragment approach in the formation of molecular models for excited electronic states and parametrization of these molecular fragments by modeling conventional (one-dimensional) absorption and fluorescence spectra of polyatomic molecules. All matrix elements that are required for calculations of the spectra can be found by the methods developed. The time dependences of the populations of a great number (>10³) of vibronic levels can be most conveniently found by using the iterative numerical method of integration of kinetic equations. Convenient numerical algorithms and specialized software for PC are developed. Computer experiments showed the possibility of the real-time modeling three-dimensional spectra of polyatomic molecules containing several tens of atoms.     

Improvement of the parametric method of the theory of vibronic spectra of polyatomic molecules: Absorption spectra and the structure of butadiene, hexatriene, and octatetraene in the excited state

The structure of the excited states and absorption spectra of butadiene, hexatriene, and octatetraene are calculated by the parametric method of the theory of vibronic spectra using models of the first-and second-order approximations. It is shown that these molecular models adequately reflect the molecular structure and allow one to predict quantitatively the shape and fine vibrational structure of the absorption spectra. When passing to the second-order approximation, only two additional (angular) parameters are used. These parameters are transferable in the series of polyenes. Compared to the first-order approximation model, the second-order approximation model more accurately takes into account the angular deformations of polyenes upon their excitation and describes the intensity distribution in the vibrational spectrum, including weak lines. In addition, the calculations also quantitatively predict spectral variations in the molecular series. The parametric method is more efficient for modeling polyatomic molecules in the excited states and their vibrational spectra compared to other semiempirical and ab initio methods.     

A semi-empirical method for the calculation of spin—orbit splitting in degenerate electronic states of linear polyatomic molecules

A semiempirical method for the calculation of spin—orbit coupling constants in linear polyatomic molecules is discussed. The method uses the readily available output from a CNDO/2 calculation and a set of effective atomic coupling constants obtained from observed spectroscopic data on atoms. Two procedures for obtaining the spin—orbit splitting are discussed: one based on a closed shell CNDO/2 calculation and one based on an open shell calculation.The average error for the molecules studied was 6.8% and 7.7% for the two procedures used in the calculations, the easier closed shell procedure giving the lower percentage error. It should be noted that the largest errors occurred in the case of diatomic molecules where the error would be expected to be the greatest. Thus, the average error involved in the values of the spin—orbit splitting for polyatomic molecules is much less than 3.7% for the closed shell procedure. The method used appears to be extendable to non-linear molecules in which the only atoms off the principle symmetry axis of the molecules are hydrogen. The method should be useful in the interpretation of photoelectron spectra.     

A semi-empirical method for the calculation of spin—orbit splitting in degenerate electronic states of linear polyatomic molecules

A semiempirical method for the calculation of spin—orbit coupling constants in linear polyatomic molecules is discussed. The method uses the readily available output from a CNDO/2 calculation and a set of effective atomic coupling constants obtained from observed spectroscopic data on atoms. Two procedures for obtaining the spin—orbit splitting are discussed: one based on a closed shell CNDO/2 calculation and one based on an open shell calculation.The average error for the molecules studied was 6.8% and 7.7% for the two procedures used in the calculations, the easier closed shell procedure giving the lower percentage error. It should be noted that the largest errors occurred in the case of diatomic molecules where the error would be expected to be the greatest. Thus, the average error involved in the values of the spin—orbit splitting for polyatomic molecules is much less than 3.7% for the closed shell procedure. The method used appears to be extendable to non-linear molecules in which the only atoms off the principle symmetry axis of the molecules are hydrogen. The method should be useful in the interpretation of photoelectron spectra.     

Quantum-mechanical calculation of the intensity distributions in spectra of resonance hyper-Raman scattering and two-photon absorption of indole and skatole

We have performed a quantum-mechanical calculation of the relative intensities of lines in the spectra of resonance hyper-Raman scattering and two-photon absorption of isolated indole, indole in an aqueous solution, isolated skatole, and skatole-water complex. The effects of hydrogen bonds and intermolecular interaction on the spectra have been considered. Particular features of the intensity distributions in the spectra of indole and skatole have been compared.     

Acetylene-Substituted Two-Photon Absorbing Molecules With Rigid Elongated Pi-Conjugation: Synthesis,Spectroscopic Properties and Two-Photon Fluorescence Cell Imaging Applications

Two asymmetrical molecules with substituted acetylene as central rigid elongated conjugation are reported as potential chromophores for two-photon microscopic imaging. These molecules consist of a typical D–π–A structure, have different donors (D), the same π-conjugated center (π) and the same acceptor (A). Structural characterization and spectroscopic properties, including single-photon (linear) absorption, quantum yields, single-photon fluorescence, and two-photon absorption spectra, were studied in solvents with different polarity. These acetylene-substituted molecules were found to have high two-photon absorption cross-sections (for example, 690 GM for molecule 1 in toluene), which were determined by a two-photon induced fluorescence method using a femtosecond Ti: sapphire laser as excitation source. Single- and two-photon cellular imaging experiments demonstrate that the substituted acetylene derivatives could be one kind of promising two-photon fluorescence probes for cellular imaging.     

Characteristic features of electronic and vibrational spectra of free polyatomic molecules

The functional relationships between the basic characteristics of individual bands of electronic and vibrational spectra of free polyatomic molecules are ascertained. These basic characteristics are the position of the maximum of an individual electronic-vibrational band, the rate of the temperature shift of the maximum of a band, the half-width of a homogeneously or heterogeneously broadened electronic-vibrational band, the rate of the temperature variation of the half-width of a band, the asymmetry parameter of a heterogeneously broadened band, and the conditions for symmetric or asymmetric distribution of the intensity over the contour of a spectral band. The interrelations between the basic spectral characteristics result from the sequential mechanism of formation and broadening of individual bands of electronic and vibrational spectra of free polyatomic molecules. It is shown that the investigation of the basic spectral characteristics of electronic-vibrational bands and their interrelations allows one to elucidate the nature of the internal motion determining the optical properties of polyatomic molecules.     

Methods for calculation of ir intensities in polyatomic molecules: A comparative study

Various methods for calculating intensities in ir spectra of polyatomic molecules are reviewed against the current theory of small vibrations of polyatomic molecules. The valence optical theory based on the representation of the molecular dipole moment as the sum of dipole moments of bonds has been shown to be erroneous. Of the two calculation procedures which use no assumptions on the molecular dipole moment, the Mayants-Averbukh method is shown to have certain advantages over the polar tensor method.     

双光子吸收材料二苯乙烯衍生物的合成及光谱性质

设计、合成并用红外光谱、1H NMR、元素分析表征了三种用于双光子吸收材料的二苯乙烯衍生物,4,4′-双(二苯氨基-反式-苯乙烯基)联苯(BPSBP),4,4′-双(二乙氨基-反式-苯乙烯基)联苯(BESBP)和4,4′-双(9-咔唑基-反式-苯乙烯基)联苯(BCSBP)。实验结果表明三者最强的单光子吸收出现在350～400 nm之间,且单光子吸收和荧光光谱中表现出明显的溶剂化显色效应,揭示了分子内对称电荷转移的本质,双光子荧光光谱则揭示了单光子和双光子吸收具有相同的发射机理。利用双光子上转换荧光法测试发现,三种双光子吸收材料在800 nm飞秒激光的激发下具有较大的吸收截面,分别为892,617和483 GM,这表明在双光子领域有潜在的应用价值。     

硅的间接跃迁双光子吸收系数谱

利用皮秒Nd:YAG脉冲激光器作为激发光源,测量出光子能量介于1.36 μm (0.912 eV)—1.80 μm (0.689 eV)之间的硅间接跃迁双光子吸收系数谱.尽管此波段范围内的激光光子能量小于硅间接带隙,但当激光辐照在硅基光电二极管受光面时,在二极管两电极端仍然探测到了显著的脉冲光伏信号.光伏信号峰值强度与入射光强呈二次幂函数关系,表明其是双光子吸收过程.采用pn结等效结电容充放电模型,将光伏响应信号峰值与入射光强相关联,从中提取出硅的间接跃迁双光子吸收系数,改变入射波长得到系数谱.研究表明:     

Method for assigning absorption bands in IR spectra of polyatomic molecules with respect to internal vibrational coordinates

A method is proposed for assigning absorption bands in IR spectra of polyatomic molecules. An algorithm is developed and a Fortran program is written based on this method. The method is illustrated for the example of the toluene molecule. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 169–173, March–April, 2007.     

Isotope shift in the spectrum of multiquantum absorption of nitromethane molecule in intense IR fields

The effect of isotope shift has been revealed in the spectra of absorption and dissociation of polyatomic molecules in an intense IR field, with no isotope shift present in the spectrum of linear absorption of a vibration being excited. The effect has been applied to separation of nitrogen isotopes in the nitromethane molecule. The effect considered increases considerably the number of molecules suitable for isotope separation by IR laser radiation.