Direct observation of the optical anisotropy of C70 fullerene molecules in the Shpol’skii spectra

Linear optical absorption and emission spectra of C₇₀ fullerene molecules in single-crystal toluene are investigated. It is established that the lines of purely electronic S ₀-S ₁ transitions are significantly polarized. The degree of linear polarization of the spectral lines depends on the position of the fullerene molecule in the toluene matrix and can be as high as 100%. The polarization characteristics of the lines can be understood in the context of a model in which the S ₀ → S ₁ electronic transition is represented by the excitation of a planar oscillator whose axis is oriented along the principal axis of the C₇₀ molecule. The relationship between the polarization of the spectral lines and the position of the fullerene molecule in the matrix is consistent with the conclusions drawn from a theoretical analysis of different configurations possible upon the embedding of C₇₀ molecules into crystalline toluene.     

Spectral and luminescent properties of jet-cooled dinaphthofuran

The fluorescence and fluorescence excitation spectra of jet-cooled dinaphtho[2,1-b:1′,2′-d]furan (dinaphthofuran) molecules, as well as their complexation with inert gases Ar, Kr, and Xe, are studied. The indicatrices of the degree of polarization of fluorescence of dinaphthofuran molecules upon excitation of the electronic transitions S ₀?S ₁ and S ₀?S ₂ are calculated as functions of the intramolecular orientation of the transition dipole moments. The fluorescence polarization spectrum is measured under excitation within the rotational contour of the line of the purely electronic transition v ₀ ⁰ = 29 294 cm^?1. In contrast to complex planar molecules, the S ₀?S ₂ fluorescence excitation spectrum of dinaphthofuran is found to be continuous, with the Q branch of the rotational contour being absent. The fluorescence excitation spectra of van der Waals complexes of dinaphthofuran with inert gases exhibit multiplet lines, which is associated with the helical structure of the molecules studied.     

Fluorescence and fluorescence excitation spectra of jet-cooled carbazole

The fluorescence excitation spectra of jet-cooled carbazole molecules at vibrational temperatures of 55 and 80 K and the fluorescence spectrum of these molecules excited by radiation at the frequency of a pure electronic transition are measured. As the vibrational temperature increases, the excitation spectra exhibit a series of lines of the same symmetry, which are caused by the interaction of the active vibration with a subensemble of optically inactive vibrations. The final symmetry of the totally and nontotally symmetric vibrations is determined from the shape of the rotational contours of the lines of vibronic transitions. The values of a decrease in the frequency of the nontotally symmetric vibrations in the first excited electronic state S ₁ due to their interaction with the electronic state S ₂ are calculated to be up to 100 cm^?1. The frequencies of the pure electronic transitions in the absorption and fluorescence spectra coincide with each other and are equal to 30809 cm^?1, the frequencies of vibrations in the ground state S ₀ exceeding the frequencies of the corresponding vibrations in the excited state S ₁. The degree of polarization of the integral fluorescence is determined for a series of vibronic transitions of the a ₁ and b ₂ final symmetry that are observed in the fluorescence excitation spectra, and the contribution of the intensity with the borrowed polarization θ_⊥ to the integral fluorescence is calculated. It is found that the intensity θ_⊥ is higher for the transitions of the b ₂ symmetry and can reach ≈50%.     

Two field nonlinear Faraday rotation in rubidium vapor in a Doppler-free geometry

Nonlinear Faraday rotation with counter-propagating light beams was investigated in a rubidium vapor cell. Observations across all hyperfine and crossover resonances of the D₂ line of ⁸⁷Rb atoms were made. Additionally, rotation spectra as a function of pump and probe intensity, pump polarization and external magnetic field strength were studied.The investigations were performed in a regime where the pump beam power was sufficiently low relative to the probe power to avoid polarization rotation due to pump-induced anisotropy. Our results are analyzed in the context of Bennett structures and coherent optical processes.     

Spectator and participator processes in the resonant photon-in and photon-out spectra at the Ce L3 edge of CeO2

We study both theoretically and experimentally the photon-in and photon-out spectra of CeO₂, which are caused by the Ce 2p to Ce 5d excitation followed by the three different de-excitation channels: (i) Ce 3d to Ce 2p (denoted by 3d-RXES), (ii) O 2p to Ce 2p (v-RXES), and (iii) Ce 5d to Ce 2p (RIXS). In 3d- and v-RXES, the 5d electron plays a role of a spectator, but in RIXS it is a participator. By extending our single impurity Anderson model (SIAM), which was used recently for our calculations of v- and 3d-RXES spectra of CeO₂, we study the polarization dependence in the spectator and participator spectra, and we perform more detailed calculations for 3d- and v-RXES spectral features, as well as new calculations for the RIXS spectrum with charge transfer excitations. The polarization dependence is different for the spectator and participator spectra; we have no polarization correlation between the incident and emitted photons for the spectator spectra but a strong polarization correlation for the participator spectrum. The theoretical calculations predict that the charge transfer excitations in RIXS occur in the transfer-energy range overlapped with v-RXES, but the RIXS and v-RXES spectra can be discriminated by taking advantage of the different polarization dependence. The overlapped RIXS and v-RXES spectra are observed successfully by our experiments and well reproduced by our SIAM calculations.     

Measurement of nanoparticle temperature in a (CO2) N cluster beam using SF6 molecules as tiny probe thermometers

A temperature measurement technique using SF₆ molecules as tiny probe thermometers is described, and results are presented, for large (CO₂) _N van der Waals clusters (with N ≥ 10²) in a cluster beam. The SF₆ molecules captured by (CO₂) _N clusters in crossed cluster and molecular beams sublimate (evaporate) after a certain time, carrying information about the cluster velocity and internal temperature. Experiments are performed using detection of these molecules with an uncooled pyroelectric detector and infrared multiphoton excitation. The multiphoton absorption spectra of molecules sublimating from clusters are compared with the IR multiphoton absorption spectra of SF₆ in the incoming beam. As a result, the nanoparticle temperature in the (CO₂) _N cluster beam is estimated as T _cl < 150 K. Time-of-flight measurements using a pyroelectric detector and a pulsed CO₂ laser are performed to determine the velocity (kinetic energy) of SF₆ molecules sublimating from clusters, and the cluster temperature is found to be T _cl = 105 ± 15 K. The effects of various factors on the results of nanoparticle temperature measurements are analyzed. The potential use of the proposed technique for vibrational cooling of molecules to low temperatures is discussed.     

Polarized Fluorescence of Jet-Cooled indole and Carbazole and Their Complexes with Water

The spectra of the fluorescence excitation within the rotational contours of the bands of the pure electronic long-wavelength S ₀-S ₁ transitions of jet-cooled indole and carbazole molecules and their complexes with water are measured. For the carbazole-water complex, a contour with three maxima is registered, which is possibly related to the occurrence of two isomers, differing in a slight displacement of hydrogen between the nitrogen atom of the imine group of carbazole and the oxygen atom of the water molecule. The degrees of polarization of integral fluorescence upon excitation within the rotational contours of the S ₀-S ₁ electronic transition bands of the above molecules and their complexes with water are determined for the first time. The coincidence of the calculated (7.7%) and measured (7.3%) values of the degree of polarization upon excitation in the rotational Q branch of the ^b L ₁-A electronic transition of indole confirms the accepted intramolecular orientation of the transition dipole moment at an angle of 38.3° with respect to the principal axis of inertia A. Upon excitation of indole, its complex with water, and carbazole into the P and R branches, the measured and calculated degrees of polarization are also close to each other and amount to 2–3%. This confirms the occurrence of contributions to the fluorescence polarization due to the rotations of the indole molecules around the principal axes of inertia A and C.     

Convergence of the reduced Hamiltonian with centrifugal distortion in asymmetric top molecules

It is shown that the goodness of fit of observed spectra of asymmetric top molecules, when using the reduced Hamiltonian of Watson, can be affected by the choice of molecular z-axis. The spectra of carbonyl fluoride and sulphur dioxide are used to illustrate this effect, and the convergence properties of the Hamiltonian are related to the order of magnitude of the co-efficient s₁₁₁ used in the contact transformation.     

The model of the optical switching center and the polarization anomalies in absorption spectra of cupric oxide after fast particles irradiation

We consider the model of the optical switching center—a system with the following properties: it has two (or more) metastable states |1〉, |2〉, separated by a potential barrier U; it can switch from one state to another by absorbing the photons with energy ?ω∼U; the transition |1〉→|2〉 is allowed only for a certain light wave polarization p₁ and the transition |2〉→|1〉—for other polarization p₂; these polarizations p₁, p₂ are orthogonal. The optical properties of this system are studied and are found to exhibit unconventional polarization dependence. In particular, the absorption spectrum observed in natural (unpolarized) light can display new features, that are absent in the spectra, obtained in two independent polarizations. We discuss these results in connection with the (yet unexplained) experimental findings [N.N. Loshkareva, Yu.P. Sukhorukov, B.A. Gizhevskii, A.S. Moskvin, T.A. Belykh, S.V. Naumov, A.A. Samokhvalov, Phys. Solid State 40 (1998) 383], where the similar anomalous polarization dependence of the absorption spectra of cupric monoxide CuO after the fast particle bombardment is reported.     

Electronic excitation in phosphorus-containing molecules. II. Inner shell electron energy loss spectra of PF5, OPF3 AND OPCl3

Electron energy loss Spectroscopy has been used to obtain the inner shell excitation spectra of PF₅, OPF₃ and OPCl₃ in the P 2p,2s (L-shell) region as well as in the respective ligand K shell (F 1s, O 1s) and L shell (Cl 2p and 2s) regions. The spectra are compared and contrasted with earlier reported spectra obtained on the trivalent phosphorus compounds (PH₃, PCl₃, PF₃ and P(CH₃)₃). The spectra were obtained using an impact energy of 2.5keV and a scattering angle of about 1°. The spectra reported here are typical of molecules with electronegative ligands in that the discrete portions of the spectra show strong transitions to virtual molecular orbitais. In addition, intense features are observed at or just beyond the ionization edge attributable to transitions to trapped inner well states, while broad features further into the continuum can be ascribed to σ^*(P—L) shape-resonances (L = ligand). This resonance assignment was supported by a comparison with the corresponding spectra for PF₃ and PCl₃.     

Doppler-free polarization spectroscopy of diatomic molecules in flame reactions

Gas phase reactions are used to produce radicals or other molecules which can hardly be evaporated. The conditions of this production method require a sensitive spectroscopic technique if sub-Doppler spectra are to be recorded. Different techniques are discussed and Doppler-free polarization spectroscopy is shown to offer the highest sensitivity for the study of these species. First polarization spectra of the A ¹∑?X ¹∑ (1, 0) transition of BaO and the B ²∑?X ²∑ (0,0) transition of CaCl are reported.     

DNA-wrapped carbon nanotubes aligned in stretched gelatin films: Polarized resonance Raman and absorption spectroscopy study

We present the study of DNA-wrapped single-walled carbon nanotubes (SWNTs) embedded in the stretched gelatin film by the polarized resonance Raman spectroscopy and visible-NIR optical absorption. The polarized dependent absorption spectra taken along and normal to the stretching direction demonstrate a comparatively high degree of the alignment of isolated SWNTs in the gelatin matrix. The analysis of Raman spectra of isolated SWNTs in the gelatin stretched films showed that the degree of the alignment of carbon nanotubes along the stretching direction is about 62%. The dependence of the peak position of G⁺-band in Raman spectra on the polarization angle θ between the polarization of the incident light and the direction of the stretching of films was revealed. This shift is explained by the different polarization dependence of the most intensive A and E₁ symmetry modes within the G⁺-band. The performed studies of embedded DNA-wrapped nanotubes in the gelatin film show the simple method for obtaining the controlled ordered biocompatible nanotubes inside a polymer matrix. It can be used for manufacturing sizable flexible self-transparent films with integrated nanoelectrodes.     

Fine-structure spectroscopy of 2-methylnaphthalene cooled in a supersonic jet

The fluorescence and fluorescence excitation spectra of 2-methylnaphthalene molecules cooled in a supersonic jet are measured. The frequencies of vibrations in the S ₀ and S ₁ states, as well as the relative intensities of electronic-vibrational transitions in the fluorescence and fluorescence excitation spectra, are calculated with the semiempirical MO/M8ST method. The intensities are calculated in the Franck-Condon approximation taking into account the mixing of all the 38 totally symmetric normal vibrations. Based on the calculations, most observed spectral lines are assigned. It is shown that the calculation accuracy of the method is high enough for it to be used to interpret the spectra of molecules of aromatic compounds such as substituted naphthalenes. It is found that the main contribution to the fluorescence spectrum is made by four optically active vibrations.     

一种测量吸附分子列向的方法——利用近阈结构谱和选择定则

局域分子轨道不易受环境影响,因此当分子被吸附且未被破坏时,跃迁到局域分子轨道产生的近阈结构谱基本不受环境影响.对于固定列向的吸附分子,当用偏振X射线测量其近阈结构谱时,相对强度将与偏振方向和分子列向有关.根据这一特性,基于选择定则可以判断吸附分子的列向. 关键词： 量子数亏损理论 近阈结构 选择定则 分子列向     

Polarization spectroscopy of Rb and Cs

Theoretical calculation of ⁸⁵Rb and ¹³³Cs D₁ signals in polarization spectroscopy is presented by using the method of velocity-selective optical pumping in a four-level system. Since good agreement between theory and experiment has been found in Na D₁ polarized signals, the theoretical calculation can be also applied to Rb and Cs D₁ lines. Rb and Cs atoms have higher total angular momentum F in the hyperfine structures than Na atom and then the calculation is more complicated. The relative signal intensities in polarization spectroscopy are compared with those in saturation spectroscopy.     

The geometric structure of pure SF6 and mixed Ar/SF6 clusters investigated by core level photoelectron spectroscopy

The S 2p core level photoelectron spectra of Sulphurhexafluoride clusters have been investigated together with heterogeneous Ar/SF₆ clusters, created by doping Ar host clusters (with a mean size of 3600 atoms) with the molecule. Surface and bulk features are resolved both in the argon 2p and the sulphur 2p core level photoelectron spectra. For the latter level such features were only observed in the pure cluster case; a single feature characterizes the S 2p core level spectra of SF₆ doped argon clusters. From the chemical shifts, investigated with respect to SF₆ doping pressure. It can be concluded that the host clusters get smaller with increasing doping pressures and that the SF₆ molecules predominantly stay below the cluster surface, whereas the Argon core stays intact. We have neither observed features corresponding to SF₆ on the cluster surface, nor features corresponding to molecules deep inside the bulk in any of the spectra from the pick-up experiments.     

X-Ray photoelectron spectrum of methylisocyanide gas

The C and N 1s spectra of methylisocyanide gas have been recorded. Two resolvable peaks of equal intensity are observed in the C 1s spectrum. Using the equivalent-cores approximation and thermochemical data, together with MNDO MO calculations and the point-charge potential model, the lower-binding-energy C 1s line is assigned to photo-emission from the isocyano carbon. The strong satellites which have been observed in the spectra of coordination complexes of alkyl and aryl isocyanides are not observed in the spectra of the free molecule. Comparisons of the point-charge-potential-corrected binding energies for C 1s and N 1s photoemissions from CH₃NC and its isomer CH₃CN with those for a host of other molecules show that photoemissions from the internal atoms in these molecules are accompanied by substantially less than average relaxation energies. These smaller relaxation energies can be understood using valence-bond theory.     

Studies of the atom-dimer polarization transfer

The polarization transfer between optically pumped alkali atoms and alkali molecules is studied, using the model introduced in a previous paper (Z. Physik A273, 9(1975)). It is shown that the atom-molecule-exchange reactionX+X ₂→X ₂+X is responsible for the nulear spin polarization observed in the alkali molecules, and that the recombination of the alkali atoms does not contribute to this polarization transfer.     

Raman scattering by zigzag fluoropolymer molecules

The Raman spectra of ultrafine powders consisting of F(CF₂)_nF fluoropolymer zigzag molecules treated as a one-dimensional nanocrystal are investigated. These spectra are compared with the Raman spectra of C_nF_2n+1Br compounds (n=6–10 and 14) and fluoroplastics. It is found that the frequencies of optical vibrations of F(CF₂)_nF fluoropolymer molecules are shifted by more than 10 cm^?1 with respect to the relevant frequencies of C₆F₁₃Br molecules. The length of nanoparticles comprising an organofluoric ultrafine powder is estimated to be L=2–2.5 nm. This estimate is obtained from the measured frequency shifts in terms of the vibrational theory for a crystalline diatomic chain of finite length.     

Polarization photosensitivity of Schottky barriers on monoclinic ZnAs<Subscript>2</Subscript> crystals

Pioneering experiments on creating Cu(In)/p-ZnAs₂ photosensitive Schottky barriers on monoclinic ZnAs₂ single crystals grown by directional crystallization from a near-stoichiometric melt are described. Photosensitivity spectra are taken from the structures in natural and linearly polarized radiations. The structures are found to be sensitive to polarization. From the photoactive absorption spectra of the monoclinic ZnAs₂, it follows that most minimal direct band-to-band transitions in these crystals are allowed in the E ∥ z axis polarization and can be used, specifically, in designing novel devices-polarization—controlled switches of spectral ranges of incident radiation photorecording.