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.     

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%.     

Spectral characteristics of heterocyclic compounds with a chain structure, cooled in an ultrasonic jet

We have recorded the fluorescence excitation spectra of three heterocyclic compounds with a chain structure [BPO (2-phenyl-5-(4-diphenylyl)oxazole), POPOP (1,4-di[2-(5-phenyloxazolyl)]benzene, and TOPOT (1,4-di[2-(5-n-tolyloxazolyl)]benzene] and the fluorescence spectra of POPOP, under conditions where the molecules were cooled in an ultrasonic helium jet. A line structure is observed in the spectra of POPOP and TOPOT; for the BPO molecules, whose configuration changes considerably during electronic excitation, vibrational structure is apparent only in the low-frequency region of the excitation spectrum, and a diffuse spectrum is recorded starting from ν ₀ ⁰ + 200 cm⁻¹. For all the compounds, in the spectra we recorded vibrations with frequencies up to 100 cm⁻¹, arising due to the flexibility of the molecular structure. The rotational contours of the lines for the electronic and vibronic transitions of the POPOP molecules (T_rot = 10.5 K) and TOPOT molecules (T_rot = 15 K) are structureless and bell-shaped. The degree of polarization of the fluorescence P_fl for the jet-cooled POPOP molecules for excitation of vibrations along the absorption band up to 2000 cm⁻¹ above ν ₀ ⁰ is practically constant (∼8.4%) and matches P_fl for high-temperature vapors. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 728–734, November–December, 2006.     

Indole in Argon Matrix: The Near UV Spectra.

Abstract

The near UV absorption, steady-state polarized fluorescence excitation and time–-resolved fluorescence emission spectra of indole in argon matrix are reported. The absorption maxima of the four lowest singlet transitions were identified at 35095 cm^?1(also the S_{1, 0} 0–0 band), 37650 cm^?1 (S_2,0), 47415 cm^?1 (S_3,0), and 51680 cm^?1 (S_4,0). No distinct 0–0 band of the second transition was identified but the linearly polarized, steady-state fluorescence excitation spectrum indicates an onset of weak S_2,0 bands on the blue side of the S_1,0 0–0 peak (35095 + 400 cm^?1). Only one fluorescence emission component, of 4.9±0.2 ns, was obtained by excitation over the S_{1, 0} 0–0 + 565 cm^?1 to S_1,0 0–0 - 245 cm^?1 domain. The reported data strongly suggest the ¹L_b ^?1A₁ and ¹L_a ^?1A₁assignment for the lowest and next lowest transitions, respectively.     

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.     

New S1 vibronic level assignments for s-tetrazine vapor: Polarization and lifetime measurements

New fluorescence excitation and dispersed SVL fluorescence spectra of s-tetrazine vapor in supersonic expansions of helium and argon are reported. A forbidden in-plane-polarized component of the $\text{A}\text{?}{}^1\text{B}{}_{\mathrm{3u}}\text{-}\text{X}\text{?}{}^1\text{A}{}_{\mathrm{g}}$ transition is discovered at (0, 0) + 578 cm^?1 with a type-B band contour in rotationally resolved excitation spectra obtained with a single-frequency cw ring dye laser. Linewidth measurements of single rovibronic transitions provide data to calculate lifetimes of low-lying S₁ vibronic states of the isolated molecule. Depending on the vibrational mode involved, the lifetime varies from 0.05 to greater than 1 nsec. The number of cold-band assignments in the absorption spectrum of s-tetrazine vapor now confirmed by analysis of SVL fluorescence spectra increases from three to ten.     

The Ã1A1-X̃1A1 two-photon fluorescence excitation spectrum of 1,2-difluorobenzene

The two-photon fluorescence excitation spectrum of 1,2-difluorobenzene was obtained with a tunable dye laser calibrated using a combination of the neon optogalvanic spectrum and etalon fringes. The spectrum consists only of A₁-A₁ bands but the use of linear and circular polarization divides the bands into two types. The 0⁰₀ type retains its intensity in circular polarization and, rotationally, shows little or no zero-rank contribution. The 5¹₀ (or 14¹₀) type loses much of its intensity in circular polarization and, rotationally, shows a large zero-rank contribution. These observations all accord with the trace of the two-photon transition tensor being close to zero for the 0⁰₀ type and large for the 5¹₀ type, the latter type being involved in vibronic interaction which mixes the $\text{A}\text{?}$ and $\text{X}\text{?}$ states. There is strong evidence for Fermi resonance between the 5¹ and 6¹10¹ levels. Parts of the one-photon absorption spectrum have been photographed to aid sequence identification and also to look for the 5¹₀, A₁-A₁ transition. This transition is not observed: nor is there any evidence for intensity stealing by b₂ vibrations.     

Theoretical Analysis of the Fluorescence Spectra of 7-Azaindole and Its Tautomer

The electronic—vibrational fluorescence spectra of the first, S₀ → ¹L_b, and second, S₀ → ¹L_a, electronic transitions of 7-azaindole and its tautomer for an isolated state have been calculated. Specific features of structural changes in 7-azaindole and its tautomer upon electronic excitation are determined. Vibrational spectra are assigned for the ground state, and the vibrational structure of fluorescence spectra is interpreted. It is shown that the intensity redistribution between the 6a and 6b oscillations, which is observed in the fluorescence spectrum of the S₀ → ¹L_b transition in 7-azaindole, can be explained as a result of intensity borrowing (according to the Herzberg—Teller mechanism) from the ¹L_a state.     

Spectroscopic studies of the sulphur afterglow

The afterglow emission spectrum of sulphur and argon mixture is found to consist of (a) the main band system of S₂(B³Σ^-_u?X³Σ^-_g) in the region 3200–6600 Å and (b) the atomic spectrum of argon in the 7500–9000 Å region. Although B?X bands of S₂ obtained by ordinary excitation extends from 2829 to 7100 Å, the lower wavelength limit of these bands from the afterglow is only 3200Å. It is proposed that the S₂ molecules are formed in the B³Σ^-_u state through inverse predissociation when two S atoms approach each other along the potential curve of the predissociating electronic state 1_u.     

Separation of overlapping singlet and triplet band systems in Cl2CS by LFES and MRS techniques

The visible absorption band systems of Cl₂CS have been reexamined using laser fluorescence excitation and magnetic rotation spectroscopy. Since the former is sensitive only to S₁ ← S₀ transitions and the latter primarily to T₁ ← S₀ transition, the spin multiplicities of the features in the overlapping singlet and triplet systems could be unambiguously determined. Analyses of the spectra gave new values for ν′₆ = 189 cm^?1 in the $\text{A}\text{?}$ state and ν′₁ = 923 cm^?1 in the $\text{a}\text{?}$ state. Bands with types A and C polarization were found to occur only very weakly in the $\text{A}\text{?}\text{←}\text{X}\text{?}$ spectrum in marked contrast to the corresponding system in the prototype thiocarbonyl compound, H₂CS.     

Laser spectroscopy of FeO: Rotational analysis of some subbands of the orange system

Extensive laser excitation spectra and rotationally resolved laser-induced fluorescence spectra have been recorded for the “orange system” of gaseous FeO in the wavelength regions 5790–6140 and 5580–5640 Å. Detailed rotational analyses have been performed for about $\text{20}\text{Ω}\text{′}$ substates lying between 16 350 and 18 550 cm^?1. These are found to comprise a very severely perturbed ⁵Δ_i excited electronic state with a bond length of about 1.69 Å (which is responsible for the parallel polarization of the electronic transition from the ⁵Δ_i ground electronic state) and a large number of “extra” $\text{Ω}$ substates with B′ values ranging from 0.38 to 0.50 cm^?1, which almost certainly belong to high vibrational levels of lower-lying electronic states. Evidence about the natures of the “extra” states is confusing, however, with the ⁵⁴FeO⁵⁶FeO isotope shifts apparently being in conflict with the patterns of vibrationally resolved laser-induced fluorescence. Every single $\text{Ω}$ substate that has been analyzed shows rotational perturbations of varying severity. The density and magnitude of the rotational perturbations are quite exceptional for a diatomic molecule, and result in a new type of totally chaotic diatomic spectrum. There is a remarkable similarity to the visible spectrum of NO₂: in NO₂ the complications arise from the high density of perturbing ground state vibrational levels; in FeO there is a correspondingly high density of perturbing electronic states at lower energy. The great complexity of the FeO spectrum arises because the states are in an awkward intermediate spin-coupling case which still resembles Hund's case (a) but shows strong tendencies toward Hund's case (c) coupling.     

S0 and S1 spectroscopy of jet cooled 9-cyano-10-methylanthracene: The methyl group as a molecular rotor

Jet-cooled fluorescence excitation and dispersed fluorescence spectra of 9-methylanthracene (MA), 9-cyanoanthracene (CA) and 9-cyano-10-methylanthracene (CMA) have been measured. The spectra of MA and CMA near the S₀-S₁ origin reveal a prominent torsional progression due to the hindered methyl group rotation and its torsional vibration against the aromatic ring frame. Additionally, the laser induced fluorescence LIF excitation spectrum of CMA shows the splitting of many vibrational modes.Observed positions and relative intensities of the methyl internal rotational bands were interpreted in terms of transitions calculated based on the quantum mechanical one-dimensional rotor. The low-frequency vibrational bands were interpreted also with the all electron quantum mechanical calculations within the RHF/6-31G(d,p), CIS/3-21G and CIS/6-31G(d,p) approximations. It is predicted that in the case of MA the eclipsed geometry (one C-H in the plane of the ring) is most stable in both S₀ and S₁ states. Conformation of the methyl group in CMA is suggested to change upon S₁ ← S₀ excitation (π/12 phase shift of the methyl group). The predicted energy barrier for methyl group rotation in the S₀ state of CMA is considerably higher (72 cm⁻¹) than that in the S₁ state (22 cm⁻¹). Following the present quantum mechanical calculations, the carbon atom of the methyl group belongs to the aromatic plane in the S₀ ground state but it deviates from this plane in the S₁ excited state. These in turn suggest that the calculated barrier for methyl group rotation in CMA has a 6-fold symmetry in the S₀ ground state and roughly a 4-fold symmetry in the S₁ state.     

S1-S0 fluorescence after narrow band excitation of glyoxal: Single rotational level fluorescence and a technique for deconvolution of Doppler congested absorptions

Individual rovibronic transitions are isolated at high resolution from a crowded absorption feature with a fluorescence excitation technique which is based on detection of fluorescence from one and only one rovibronic level. The method is illustrated by resolving four rovibronic transitions from the single rotational line-like feature in the 0, 0 band of the ${}^1\text{A}{}_{\mathrm{u}}\text{←}{}^1\text{A}{}_{\mathrm{g}}$ (S₁ ← S₀) absorption of glyoxal vapor. The rotational structure of the 5₁⁰ fluorescence band is studied as a function of tuning a narrow-band laser line (linewidth < 10^?4 cm^?1) to various positions in and near this absorption feature. The fluorescence structure proves an extremely sensitive tool for detecting small absorptions, with emission from 12 rovibronic levels being identified. One of the spectra so obtained is a close approximation of true single rotational level fluorescence.     

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.     

Fluorescence polarization of helical molecules cooled in a supersonic jet

The β-binaphthylene oxide molecules studied under supersonic cooling conditions have a number of specific properties due to their nonplanarity. Low-frequency vibrations of the molecules in the excited S1 state are higher than the frequencies for the S0 state, and conversely the high-frequency vibrations have lower frequencies. The S₀-S₂ fluorescence excitation spectrum is structureless. The absence of a Q branch in the rotational contour of the line for the purely electronic transition indicates that it is substantially broadened and shifted toward shorter wavelengths as a result of rotational perturbations of the helical structure of the molecule. Multiplet lines in the spectra of β-binaphthylene oxide complexes with argon, krypton, and xenon correspond to different isomeric complexes. Their bond energies are below those observed previously for planar polycyclic molecules such as perilene, fluorene, and carbazole. The greater number of isomers with xenon is due to strengthening of the bond in the van der Waals complex and the nonequivalence of the position of the xenon atoms on the outside and inside of the helical molecule. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 473–477, July–August, 2006.     

Unravelling overlaps and torsion-facilitated coupling using two-dimensional laser-induced fluorescence

Two-dimensional laser-induced fluorescence (2D-LIF) spectroscopy is employed to identify contributions to fluorescence excitation spectra that arise from both overlapping bands and coupling between zero-order states (ZOSs). Evidence is found for the role of torsional motion in facilitating the coupling between vibrations that particularly involves the lowest-wavenumber out-of-plane vibrational modes. The experiments are carried out on jet-cooled p-fluorotoluene, where the molecules are initially in the lowest two torsional levels. Here we concentrate on the 390–420?cm^?1 features in the S₁?←?S₀ excitation spectrum, assigning the features seen in the 2D-LIF spectrum, aided by separate dispersed fluorescence spectra. The 2D-LIF spectra allow the overlapping contributions to be cleanly separated, including some that arise from vibrational-torsional coupling. Various coupling routes open up because of the different symmetries of the lowest two torsional modes; these combine with the vibrational symmetry to provide new symmetry-allowed vibration-torsion (‘vibtor’) interactions, and the role of the excited m?=?1 torsional level is found to be significant.     

Investigation of the octaethylporphin cationic forms in a silicate gel matrix by methods of low-temperature site selective spectroscopy

The spectral-luminescent properties of an octaethylporphin-doped inorganic xerogel prepared from tetraethoxysilane by the sol-gel method have been investigated. With the help of selective excitation and selective monitoring of fluorescence, it has been established that the octaethylporphin molecules, on their embedment into the gel matrix, form two cationic forms, dicationic and monocationic; the longest wavelength absorption band of the latter is shifted to the red. The significant influence of the gel matrix on the energy of the excited electronic Q states (S₁ and S₂) is shown. By the fluorescence line narrowing method at 4.2 K, fine-structure fluorescence and fluorescence excitation spectra of both forms have been obtained; the frequencies of the normal modes in the S₀ and S₁ states have been determined. The data on vibrational frequencies are interpreted on the basis of their juxtaposition with those from the fluorescence line narrowing spectrum of octaethylporphin and resonance Raman spectra of its complexes with copper and nickel. Cases of the appearance of out-of-plane vibrations in the fluorescence spectra have been revealed; their activation is explained by the nonplanarity of the porphyrin macrocycle for the cationic forms.     

High-resolution laser excitation spectra of linear triatomic molecules: Analysis of the B2Σ+-X2Σ+ system of SrOH and SrOD

Single-mode cw dye laser excitation spectra of the (0, 0⁰, 0)-(0, 0⁰, 0), (1, 0⁰, 0)-(1, 0⁰, 0), (0, 1¹, 0)-(0, 1¹, 0) bands of the 611- to 607-nm system of SrOH and SrOD were observed and assigned. The spectrum is consistent with a ²Σ-²Σ system where the molecule is linear in both electronic states. The rotational analysis is obtained by measuring P-R separations in the excitation spectrum. A technique which greatly aided in the spectral assignment that utilizes a monochromator as a bandpass filter in obtaining excitation spectra is described. A new spin-rotation constant, γ⁽⁺⁾ - γ^(?), was found necessary to fit the l-type doubling of the (0, 1¹, 0) mode in B²Σ⁺ of SrOH. This new constant is assumed to arise from two ${}^2\text{Σ}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ vibronic states, split by Renner-Teller interaction, of the (0, 1¹, 0) mode of A²Π. From a perturbation treatment of this electronic interaction, ?ω₂ of the (0, 1¹, 0) mode of A²Π was found to be 14 cm^?1. The linear structure of SrOH and SrOD in both electronic states is consistent with the model, in the one-electron approximation, in that the transition involves the promotion of the unpaired 5s to the 5p orbital localized on the strontium.     

Spectral-Luminescence Characteristics of Carbazole, Dibenzofuran, and Dinaphthofuran in the Gas Phase in Excitation by Electrons and Photons

The spectra of electron-energy loss, the excitation functions, and the fluorescence spectra in excitation of carbazole, dibenzofuran, and dinaphthofuran by monoenergetic beams of electrons of different energies are determined. The singlet-triplet transitions S ₀–T ₁ and the singlet-singlet transitions up to S ₀–S ₇ are recorded, which covers the region 2–11 eV. In the spectra of electron-energy loss, bands that refer to the n^ast and ^* transitions are identified. The replacement of the heteroatom of nitrogen by the atom of oxygen in the five-membered ring has no substantial effect on the spectra of electron-energy loss.     

Direct observation of proton transfer from the excited <Emphasis Type="Italic">S</Emphasis><Subscript>2</Subscript> state in the 3-hydroxyflavone molecule

The spectra of dual fluorescence of 3-hydroxyflavone molecules excited by 44-ps pulses in the region of the S ₁ and S ₂ absorption bands are measured with a picosecond resolution. The dynamics of the spectra directly demonstrates the time development of the proton transfer from the carboxyl to the carbonyl group of the molecule. Upon excitation into the main absorption band, the transfer process occurs for about 210 ps. The excitation into the region of the S ₂ band results in a faster (～170 ps) process, and the relative contribution made to the total spectrum by the long-wavelength band, which belongs to the proton-transfer state, is higher in this case for all the time ranges of luminescence recording. The data obtained directly point to an additional channel of proton transfer via the S ₂ state. The probability of this process is estimated to be 0.84 × 10¹² s^?1.