Fermi-type resonance in quasi-linear fluorescence excitation spectra of triazatetrabenzoporphine

The effect of deuteration of the central NH groups on the quasi-linear fluorescence and fluorescence excitation (with selective monitoring) spectra for triazatetrabenzoporphine, a close analog of phthalocyanine, has been investigated at 77K in n-nonane. Vibrational analysis of the spectra was carried out. The normal mode frequencies were determined for the electronic states S₀ (from fluorescence spectra) and S₁ (for fluorescence excitation spectra). It has been established that N-deuteration lowers the frequency of a vibration involving inplane NH bending down to ∼990 cm⁻¹ and leads to resonant vibrational-electronic (vibronic) interaction of Fermi-type resonance between the zero level of the S₂ state and the vibronic level of the S₁ state upon excitation of this mode. Thereby the possibility of the “vibronic analog of Fermi resonance” (a term coined by G. Herzberg) occurring in a simple (two-component) variant of phthalocyanine-type molecules has been shown. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 6, pp. 796–803, November–December, 2008.     

Effect of Deuteration on Quasiline Electronic‐Vibrational Spectra of Phthalocyanine

Quasiline electronicvibrational spectra of fluorescence and absorption (excitation of fluorescence in selective recording) of the molecules of phthalocyanine deuterated around the periphery of benzene rings (H₂Phcd ₁₆) and the center of the macrocycle (D₂Phc) are obtained. The vibrational frequencies of the ground state are almost insensitive to this deuteration (except for vibrations with the participation of angular deformations). In excitation spectra, changes in deuteration are more pronounced due to the effects of nonadiabatic vibronic interaction of the vibrational sublevels of the S ₁ state and of the purely electronic level S ₂.     

Concentration dependence of photoluminescence properties in poly[(2-methoxy,5-octoxy)1,4-phenylenevinylene] thin films

Photoluminescence and selective excitation photoluminescence measurements at room temperature have been performed on poly[(2-methoxy,5-octoxy) 1,4-phenylenevinylene] (MO-PPV) thin films, which are prepared from MO-PPV chloroform solutions of different concentrations. The position of the S0→S1 absorption peak shows red-shift and broadened relative to that in an MO-PPV solution form due to the solidification effect, while no relative shifts between the absorption spectra of these film samples are observed. A long wavelength emission component near 630 nm has been identified as S2→S0 vibronic transition through the Gaussian decomposition method and confirmed by below-gap PL and selective-excitation PL experiments. This second vibronic component cannot be observed in the spectra of thick films. The PL efficiency of MO-PPV thin film is also investigated through comparison with that of an MEH-PPV thin film and explained by the side substituent effect.     

Vibronic states in single molecule electron transport

A scanning tunneling microscope was used to study the electron transport through individual copper phthalocyanine molecules adsorbed on an ultrathin Al(2)O(3) film grown on a NiAl(110) surface. The differential conductance spectra display series of equally spaced features, which are attributed to vibronic states of individual molecules. The coupling of the electron current to the vibronic modes was observed to depend on the structures of the adsorbed molecules. Vibronic features were not observed for molecules adsorbed on the bare NiAl(110) surface due to spectral broadening.     

1-甲基萘的振动分辨激光诱导荧光光谱研究

在超声射流条件下得到了1-甲基萘的激光诱导荧光光谱,并结合理论计算研究了1-甲基萘分子的基态和激发态的几何构型及振动信息.运用DFT方法在B3LYP/6-311++G*的水平上优化了1-甲基萘的基态儿何构型,结果表明1-甲基萘分子基态的S-E和E-S两个构象体中,只有S-E构象体为稳定构型,E-S构象是连接两个S-E构...     

聚合物MO-PPV薄膜光致发光特性研究

研究了新型PPV衍生物聚对(2－甲氧基－5－辛氧基)苯撑乙烯, （Poly［(2-methoxy,5-octoxy)1,4-phenylenevinylene］,MO-PPV)在薄膜态下的光致发光特性.对不同浓度MO-PPV的氯仿溶液制备的薄膜样品,在室温下测量了其荧光光谱,观察到MO-PPV在长波有一个“肩”型特征的发射峰.在对其采用曲线拟合的基础上,进一步对薄膜样品的带隙下激发谱和选择激发荧光谱进行了分析,从实验上论证了长波段的发射峰来自于激发态S1到基态S0的振转跃迁,排除了薄膜聚集体和激基缔合物发光的可能性.并基于不同浓度样品中Frank-Condon因子的强度变化,对各发射峰强度的变化进行了分析.     

Electronic spectra of cationic forms of meso-tetrapropylporphin in a nanoporous silicate gel matrix

We have studied the fluorescence and fluorescence excitation spectra at 300 K, 77 K, and 4.2 K for silicate gel matrices colored with meso-tetrapropylporphin by impregnation of the matrix with a solution of the pigment. Comparison of the data obtained with the absorption spectra in acidified solutions and analysis of the low-temperature fine-structure vibronic spectra, and also taking into account data obtained earlier for octaethylporphin in a xerogel showed formation of two cationic forms of meso-tetrapropylporphin in the gel matrix: the short-wavelength form has a dicationic structure, while the long-wavelength form has a monocationic structure. We have traced out the correlations of the vibrational structure in the spectra of the dicationic form with data for the porphin dication, and we have drawn a number of conclusions concerning the normal vibrational modes that are active in the vibronic fluorescence and absorption spectra of the studied cationic forms. Using the AM1 semiempirical quantum chemical method, we optimized the geometry of the mesotetrapropylporphin dication: the most stable of the possible conformers is the dication structure with saddleshaped macrocycle nonplanarity. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 453–461, July–August, 2006.     

Low-temperature spectroscopy of organic molecules in solids by photochemical hole burning

Characteristic features of photochemical hole-burning (PHB) in the impurity spectra of low-temperature solids and PHB applications in molecular spectroscopy are considered. The evolution of a no-phonon hole and a phonon sidehole in excitation and fluorescence spectra is analysed on the basis of model calculations. Some more complex models for PHB are considered, which take into account reverse reactions, the optical thickness of the sample, the inhomogeneous dispersion of both homogeneous linewidths and transition energies of the photoproduct and quasi-static impurity-impurity interactions. The effects of PHB on fluorescence line narrowing are discussed. By PHB homogeneous linewidths of purely electronic and vibronic no-phonon lines in the spectra of some porphine and phthalocyanine derivatives in various matrices are measured and their temperature dependence is studied. The latter is found to be essentially different in polycrystalline and glassy matrices. Line-broadening mechanisms are discussed. By PHB the existence of an inhomogeneous distribution of vibrational frequencies in molecular impurities is established. The applications of PHB in the studies of photochemical reactions in solid solutions of phthalocyanine derivatives and tetracene are regarded and the mechanisms of these reactions are discussed. The results obtained by PHB for chlorophyll and its derivatives are presented.     

Gas phase electronic spectrum of the HSCCS radical by laser-induced fluorescence spectroscopy

In a discharged supersonic jet of a CS₂ and C₂H₂ mixture, a vibronic band system of a new radical species was observed in the energy region 21 800-23 000 cm⁻¹ by laser-induced fluorescence (LIF) spectroscopy. The LIF excitation spectrum shows progressions with 490 and 80 cm⁻¹ separations. The vibronic structure of a dispersed fluorescence (DF) spectrum, obtained by tuning a probe laser to the vibronic origin band, also consists of progressions with 520 and 100 cm⁻¹ separations. A high-resolution laser scan provided a rotationally resolved LIF excitation spectrum for the vibronic origin band, showing the rotational structure of a-type transitions of a near-prolate top. Several chemical tests indicate that the spectral carrier contains sulfur atom(s), one hydrogen atom and more than one carbon atoms. Electronic transition energy, vibrational frequencies, and rotational constants of this species are similar to those of SCCS⁻ [M. Nakajima, Y. Yoneda, Y. Sumiyoshi, T. Nagata, Y. Endo, J. Chem. Phys. 119(2003)7805-7813.], and the spectral carrier was assigned as an isoelectronic radical, bent HSCCS. Ab initio geometrical optimizations supported the spectral carrier to be HSCCS. The observed electronic transition was assigned to be the transition, which corresponds to the Π-Π transition in the limit of linear geometry. The observed vibrations in the excitation and DF spectra were assigned as the symmetric CS stretching (ν₅) and SCC bending (ν₇) modes by comparing the results of theoretical calculations.     

Electron-vibron coupling in high-resolution X-Ray absorption spectra of organic materials: NTCDA on Ag(111)

We report additional rich fine structures in high-resolution near-edge x-ray-absorption fine structure (NEXAFS) spectra of large organic molecules using NTCDA on Ag(111) as an example. These fine structures are completely interpreted as vibronic coupling to electronic core excitations. The coupling is mode selective; predominantly one vibronic mode couples to each excitation. The fit results suggest the occurrence of a Davydov splitting, first observed for core excitons. Morphological differences substantially influence the electron-vibron coupling, indicating a strong intermolecular interaction. Thus NEXAFS becomes a more subtle probe for organic solids.     

Photon echo experiments on 3–3′ diethylthiacarbocyanine in glass-forming liquids with ultrafast laser pulses

Summary  Photon echo experiments on diethylthiacarbocyanine iodide (DTCI) in dibuthylphthalate (DBP) and glycerol in the glass phase with femtosecond pulses are presented. The PE signal shows nonexponential decays even at low temperatures. This behavior is attributed to the many vibronic resonances of the chromophore/ glass system which can be simultaneously excited by the spectral bandwith of the laser pulses. We are able to extract from the PE decays the contribution of the homogeneous dephasing rate of the 0-0 transition of DTCI up to 20 K in dibutylphthalate and 40 K in glycerol. A beating structure in the echo decay for the system DTCI/DBP is also observed from 8 K up to 180 K (glass transition temperature for DBP). This feature is attributed to an intereference process involving excitation of a vibronic transition of DTCI characterized by a vibrational frequency of 300 cm^-1.     

Yb:FAP和Yb:C_3S_2-FAP晶体光谱的温度特性和选择激发

报导了Yb :FAP和Yb :C3S2 _FAP晶体在不同温度下的吸收光谱和荧光光谱实验结果 ,研究发现由于电子_声子近共振耦合作用 ,Yb :FAP和Yb :C3S2 _FAP晶体均存在有明显的振动谱 ,Yb :FAP晶体的零声子线在低温下还劈裂为相差 10cm- 1 的两条线 .采用激光选择激发技术研究了Yb3 离子在FAP和C3S2 _FAP晶体中的格位特征 ,结果表明Yb3 离子在这两种基质中都只占据Ca(Ⅱ )格位 ,但由于CaF2 的挥发 ,导致了Ca(Ⅱ )格位的局部畸变 .     

Excited-state dynamics of magnesium phthalocyanine thin film

Ultrafast excitation relaxation dynamics of magnesium phthalocyanine (MgPc) thin film were investigated by femtosecond pump-probe spectroscopy. The excited state dynamics of MgPc's Q-band were found to be strongly dependent on the probe wavelength. Ultrafast exciton–exciton annihilation with a t^−1/2 time dependence of the excited-state population was observed.     

Laser spectroscopy of jet－cooled CuF in visible region

The laser-induced fluorescence excitation spectra of jet-cooled CuF have been recorded in the range of 19000－21470cm^{-1}, in which the CuF radicals were produced by the reaction of SF_6 with copper atoms from a dc discharge-sputtering source under supersonic jet conditions. Eight observed vibronic transition bands have been assigned as the transition from the ground state X(^1Σ^+) to B(^1Σ^+), C(^1Π) and an unreported upper state. The rotational structure of all observed bands has been analysed at the estimated rotational temperature 80K. We determined the newly observed band to be the (^1Π, v=1)－X(^1Σ^+v=0) transition according to the character of the rotational structure and the isotopic shift analysis. In addition, the lifetimes of the states involved in these bands were measured.     

Phenyl substituted Mg porphyrazines: The effect of annulation of a chalcogen-containing heterocycle on the spectral-luminescent properties

We have performed complex experimental and theoretical investigations of the spectral-luminescent properties and electronic structure of new phthalocyanine analogs, Mg octaphenylporphyrazine and its derivatives with an annulated thiadiazole or selenadiazole ring instead of two phenyl groups. Fluorescence characteristics have been determined at 293 and 77 K: emission, excitation, and fluorescence polarization spectra; fluorescence quantum yield ?? _F , and lifetime ?? _F . Annulation of a five-membered chalcogen-containing heterocycle leads to splitting of the long-wavelength absorption band Q(0-0) and to the bathochromic shift of its longest wavelength component Q _x (0-0), which increase upon passage from S to Se. At the same time, the fluorescence quantum yield ?? _F and lifetime ?? _F decrease, which is related to the intramolecular heavy-atom effect. The geometric structure of the ground state of the Mg porphyrazine molecules has been determined based on the density functional theory (DFT), and excited electronic states have been calculated with modified parametrization of the INDO/S method, INDO/Sm. Semiquantitatively, the calculated level positions of the lowest Q states and spectral shifts of Mg octaphenylporphyrazine and S-derivative agree with experimental data. For the range of the Soret band, calculated transition energies and their intensity distributions substantially depend on the dihedral angle ?? between a phenyl ring and porphyrazine macrocycle. We show that, based on calculations at the angle ?? = 60°, bands in the observed absorption spectra can be assigned with an accuracy of ??2000 cm^?1.     

Extreme narrowing of bands in the fluorescence excitation spectra of organic molecules in solid solutions

Extreme narrowing of bands in the fluorescence excitation spectra of some organic molecules is found. This narrowing is observed when the excitation spectrum of a narrow spectral interval of the fluorescence band is recorded. The effect is observed in a wide variety of matrices and permits one to determine exactly the vibronic structure of the excited electronic state of the dissolved molecule.     

Study of spectral properties of zinc phthalocyanines used as sensitizers in photodynamic therapy

Some features of the influence of the structure of water-soluble zinc phthalocyanines on their spectral parameters and state in solutions are studied. It is shown that the position of the long-wavelength electronic absorption band only weakly depends on the type of ionogen substituents in the zinc phthalocyanine macrocycle. It is found that the state of the dye in aqueous solution substantially depends on the type of a substituent in the dye macrocycle.     

Production and state-selective detection of ultracold RbCs molecules

Using resonance-enhanced two-photon ionization, we detect ultracold, metastable RbCs molecules formed in their lowest triplet state a (3)Sigma(+) via photoassociation in a laser-cooled mixture of 85Rb and 133Cs atoms. We obtain extensive bound-bound excitation spectra of these molecules, which provide detailed information about their vibrational distribution, as well as spectroscopic data on several RbCs molecular states including a (3)Sigma(+), (2) (3)Sigma(+), and (1) (1)Pi. Analysis of this data allows us to predict strong transitions from observed levels to the absolute vibronic ground state of RbCs, potentially allowing the production of stable, ultracold polar molecules at rates in excess of 10(6) s(-1).     

Laser-induced temporal and wavelength resolved spectroscopy of the 3Π-3Σ− system of matrix-isolated CNN

Detailed emission spectra, excitation frequencies, and single vibronic state lifetimes are reported for the matrix-isolated CNN radical. Discussion of the ³Π state relaxation from v′>0 (³Π) is presented in light of the observed results.