Some electronic spectra of dibenzofuran

The low-energy electronic states of dibenzofuran have been investigated by absorption and emission spectroscopy. The absolute intensity of absorption parallel to the a and b axes of a single crystal at room temperature has been measured from 32 000 to 42 000 cm^?1, and qualitative information about the strength of the c-axis absorption was obtained from a study of finely-ground dibenzofuran compressed in KBr discs. The symmetries of three transitions were determined and tentative assignments of two others were made. The absorption bands in the spectrum of the crystal held at 4.2 K remained broad, an effect attributed to exciton-phonon interaction. Spectra of dibenzofuran in a polycrystalline n-heptane matrix at 4.2 K were sharp and vibrational analyses of fluorescence and phosphorescence are given in terms of the known ground state fundamentals.     

The vapor-phase infrared and Raman spectra of p-difluorobenzene (h4) and (d4)

This new study of the vapor-phase infrared and Raman spectra of p-difluorobenzene (h₄) and (d₄) includes assignments from the high-resolution electronic spectrum, from fluorescence spectra, and one assignment from the two photon electronic spectrum. A new set of frequencies and assignments has been made for the fundamentals of this important intermediate-sized molecule. The most important changes concern the assignments previously made for the lowfrequency a_u mode (ν₈), two members of the b_2u class (ν₁₉ and ν₂₀), and one very important change for the lowest frequency fundamental of the b_3u (out-of-plane) class (ν₃₀), which has been observed directly in the far infrared. The results are all corroborated by the assignments of the perdeuterated analog where changes in previous assignments of Fermi resonance pairs have also been made. Some interesting differences between the Raman spectra of the vapor and the liquid perproto compounds have not been adequately explained in this study.     

Spectre d'absorption et effet Zeeman de l'ion Mn2+ dans un sulfate acide de manganese et de potassium MnK4H2(SO4)4, 2H2O a basse temperature

We present aborption spectra of an oriented single crystal of MnK₄H₂(SO₄)₄, 2H₂O at temperatures between 20 and 1.6 K. This salt has orthorhombic symmetry and gives, both in the visible and ultraviolet regions, an absorption spectrum which changes considerably when the temperature decreases from 20 to 4.2 K. The spectrum has sharp lines at 1.6 K in the two absorption regions corresponding to teh excited levels ⁴A₁⁴E(⁴G) and ⁴T₂(⁴D). A study has been made of the Zeeman splitting of these sharp lines; a discontinuity has been observed in the Zeeman splitting as a function of magnetic field at 1.6 K. This discontinuity is a consequence of a magnetically-ordered phase.     

Assignments of the nπ singlet states of p-benzoquinone

The vapor phase fluorescence spectra of p-benzoquinone-h₄ and d₄ are reported and discussed in relation to the assignment of the low lying singlet states. The low temperature, polarized single crystal electronic absorption spectra of p-benzoquinone and several of its isotopic derivatives are reported. From the isotope shifts and band polarizations of the various vibronic origins, a detailed vibronic analysis is offered of the electronic absorption spectrum of p-benzoquinone which indicates a near degeneracy of the ¹A_u and ¹B_1g electronic states.     

The near-ultraviolet spectrum of diacetylene trapped in solid argon at 9 K

The absorption spectra of normal and deuterated diacetylene trapped in solid argon at 9 K were investigated in the near-ultraviolet region between 2000 and 3000 Å. The vibrational structure observed at low temperature for the band system at 2448 Å, which was previously reported by Haink and Jungen in the gas phase, and identified as a ¹Δ_u ← X¹Σ_g⁺ transition, was analyzed. A comparison between the spectra for C₄H₂ and C₄D₂ suggests some revisions in the upper-state vibrational assignments. The possibility that the upper state assumes a C_2htrans configuration of ¹A_u symmetry is examined. The matrix spectra also appear to indicate that the absorption spectrum observed at 2576 Å in the gas phase and which has been assigned to a ¹Σ_u^? ← X¹Σ_g⁺ transition may not originate in the ground state of C₄H₂.     

The rotational Raman spectra and cross sections of H2O, D2O, and HDO

We report the experimental rotational Raman spectra of H₂O, and of a mixture of D₂O and HDO in the vapor phase at room temperature, and their interpretation in terms of rotational–vibrational energies, wavefunctions, and transition moments of the molecular polarizability. These transition moments are based on high-level ab initio calculations of the wavelength dependent polarizability surface, and on wavefunctions where the rotational–vibrational coupling is considered in detail. As a byproduct of this analysis several tables have been compiled including scattering strengths and assignments for individual rotational transitions of the three species. From these tables the rotational Raman spectra can be simulated over the range of temperatures up to 2000 K for H₂O, and up to 300 K for D₂O and HDO.     

Microwave spectrum,dipole moment,and structure of 3-aminopropanol

The microwave spectra of 3-aminopropanol and three of its deuterium substituted isotopic species have been investigated in the 26.5 to 40 GHz frequency region. The rotational spectrum of only one conformer has been assigned in which presumably a hydrogen bond of the OH---N type exists. The rotational spectra of a number of excited vibrational states have been observed and assignments made for some of these excited states. The average intensity ratio for the rotational transitions between the ground and excited vibrational states indicates that the first excited state is about 120 cm^?1 above the ground state.and the next higher state is roughly 200 cm^?1 above the ground vibrational state. The dipole moment was determined from the Stark effect measurements to be 3.13 ± 0.04 D with its principal axes components as |μ_a| = 2.88 ± 0.03 D, |μ_b| = 1.23 ± 0.04 D and |μ_c| = 0.06 ± 0.01 D. The possibility of another conformer where the hydrogen bond could be of NH---O type was explored, but the spectra of such a conformer could not be identified.     

The 14N quadrupole coupling constants and barrier to internal rotation of ethylcyanide-d5

The microwave spectrum of ethylcyanide-d₅ has been recorded from 18.0 to 40.0 GHz. Both a-type and b-type transitions were observed and assigned. Also, the R-branch assignments have been made for three excited states of the internal torsional mode and two excited states of the CN inplane bending mode as well as an excited vibrational state involving both of these motions. The barrier to internal rotation was determined to be 3.00 ± 0.15 kcal/mole from the E, A splittings of the third excited state. The quadrupole coupling constants of the¹⁴N nucleus were found to have values of ?3.213, 1.168, and 2.045 MHz for χ_aa, χ_bb, and χ_cc, respectively. These results are compared to those previously obtained on the corresponding hydrogen compound.     

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.     

Detection of partial inverse spinel structure in CdIn2S4 by fourier transform spectroscopy

The lattice vibrational spectrum of a single crystal of CdIn₂S₄ has been recorded at low temperature (4.2 K) by using Fourier transform spectroscopy. The absorption line corresponding to the T_1u IR active mode has been studied in detail. It has been observed that this line is split into two closely spaced lines located at 69.9 and 71.1 cm^?1. This splitting is explained on the basis of the existence of a partially inverse spinel structure.     

Vibrational spectra, normal coordinate analysis and thermodynamics of 2, 5-difluorobenzonitrile

The FTIR spectrum of 2, 5-difluorobenzonitrile has been recorded in the region 200–4000 cm⁻¹ (in liquid phase). The laser Raman spectrum in the range of 0–3500 cm⁻¹ (in liquid phase) has also been recorded. The spectra have been analyzed assuming C _s point group symmetry for the molecule. A zero-order normal coordinate analysis has been made for the molecule using force constants derived earlier. On the basis of potential energy distributions and eigen vectors unambiguous vibrational assignments have been made for all the fundamentals of the molecule. Thermodynamic functions have also been computed in the temperature range 200–1000 K by utilizing the observed fundamental frequencies assuming rigid-rotor harmonic oscillator approximation.     

The phonon densities of states of trigonal,vitreous and red amorphous selenium

For trigonal, vitreous and red amorphous Se the phonon densities of states F(hω) have been determined by inelastic neutron scattering from powder samples. For trigonal Se F(hω) is compared with the phonon dispersion measured by Teuchert[1] and a frequency spectrum derived from a model calculation by Etchepare et al.[2]. This calculation helps interpreting the changes in characteristic vibrational modes when going from the ordered to the disordered phase of Se. It is shown that at present, however, the models for trigonal Se are not good enough to calculate a reliable F(hω). The ω-dependence of F(hω) at low frequencies nicely confirms the predictions of a model which was developed for high polymeric chains by Genensky et al.[3]. For all three modifications the lattice specific heat c_v(T) was deduced from the phonon spectra. The data obtained for the different modifications are compared among each other and also with the measured data of Grosse et al.[4] (c_v(T) for red amorphous Se has not been measured before). From our data as well as from the c_p-data of Grosse the Debye temperatures as a function of temperature have been calculated. For vitreous Se between 10 and 160 K the agreement is excellent, for trigonal Se there are certain deviations which are discussed.     

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%.     

Single vibronic level fluorescence spectra from the S1(1B2u) state of p-difluorobenzene vapor

${}^1\text{B}{}_{\mathrm{2u}}\text{→}{}^1\text{A}{}_{\mathrm{1g}}$ fluorescence spectra have been obtained after pumping each of 19 bands in the S₁ ← S₀ absorption of p-difluorobenzene under collision-free conditions. The fluorescence analyses provide new assignments of some absorption bands and confirmations of others so that the assignment of the principal structure in absorption is essentially secure. Only the identity of some sequence forming modes remains unconfirmed. The assignments confirm a number of excited-state fundamentals and provide new values for others (Table I). Analysis of the weaker structure in zero-point S₁ fluorescence gives a full picture of vibrational activity in the S₁ ← S₀ transition. In so far as can be determined, the vibrational activities in fluorescence and absorption are in complete correspondence. The vibrational activity in the allowed p-difluorobenzene transition replicates to a good degree that found in the forbidden transition of benzene. Evidence suggesting a nonplanar S₁ state is found. A Franck-Condon analysis is given for progressions in three modes, and several strong Fermi resonances are identified in the S₁ state.     

Submillimeter-wave spectroscopy of HCN in excited vibrational states

Measurements of the rotational spectrum of HCN in excited vibrational states have been extended to higher-J values. The transitions reach J=8←7 around 710 GHz for most vibrational states studied in this investigation and J=22←21 near 2 THz for the (020) and (030) vibrational states. Using a pure sample of gaseous HCN at 350 K, selected states up to one quantum in the C–H stretching vibration at 3311.5 cm⁻¹ have been investigated. Even transitions having two quanta in the C–H stretch could be studied employing a glow discharge in a gas mixture of CH₄ and N₂. Molecular constants in 13 vibrational states have been obtained, several of which have been studied for the first time by rotational spectroscopy. The vibrational temperature in the discharge system is found to be about 1500 K for the stretching vibrational modes and about 600 K for the bending states.     

Influence of short-and long-range interaction forces on the efficiency of collisional vibrational energy transfer in the vibrational quasi-continuum

Based on measurements of the time-resolved delayed fluorescence, the influence of universal interactions on the collisional vibrational energy transfer is studied in mixtures of vibrationally excited polyatomic molecules (acetophenone, benzophenone, and anthraquinone) with inert bath gases (Ar, C₂H₄, SF₆, CCl₄, and C₅H₁₂). From the dependences of the decay rates of delayed fluorescence on bath gas pressure, the efficiencies of the establishment of vibrational (V-V relaxation) and thermal (V-T relaxation) equilibrium after excitation of molecules into the vibrational quasi-continuum of a triplet state are estimated. The main emphasis is on studying the dependences of the efficiency of collisional vibrational energy transfer on temperature and the molecular characteristics of collision partners. It is found that the efficiency increases with the complication of the structure of bath gases for the V-V process and decreases upon the increasing of their mass for the V-T process. For the temperature range 273–553 K, the negative temperature dependence of the V-V transfer probability and the positive (Landau-Teller) dependence of the V-T transfer probability were obtained. It is concluded that the above regularities reflect the dominant role of long-range attractive forces in initiating the quasi-resonant V-V transfer and of short-range repulsive forces in the V-T transfer of vibrational energy.     

Resonance series of Br2 in the vacuum ultraviolet

A high-resolution resonance fluorescence spectrum of bromine excited by an electrical discharge in the region 1500–2100 Å was photographed on a 10.7-m concave grating vacuum spectrograph. Twelve resonance doublet series excited by four bromine atomic resonance lines were identified and analyzed. All doublet series have the ground state of ^79,81Br₂ as the lower electronic state. The vibrational numbers of these doublets corresponding to this state vary from 0 to 76. Rotational constants are obtained by least-squares fitting of the doublet separations, and the vibrational constants by least-squares analysis of vibrational term values. Probable assignments for the upper electronic state(s) of the transitions involved were suggested.     

Magnetic field effects on the fluorescence of Cr3+ in GdAlO3

The fluorescence spectrum of Cr³⁺ in GdAlO₃ has been examined at 4.2 K as a function of magnetic field up to 60 kG. The resulting splitting of the ²E → ⁴A₂ emission lines are explained in terms of a modified molecular field approximation, which incorporates the effect of the spin fluctuations. The exchange constant in the relaxed excited state is found to be 1.2 cm^-1, which differs from that reported from absorption data. It is suggested that the difference may be related to the Frank-Condon effect.     

The Influence of Temperature on Coumarin 153 Fluorescence Kinetics

The influence of temperature varied in the range 183 K–323 K on the fluorescence quantum yield, fluorescence lifetime, absorption and emission transition moments and non-radiative deactivation rate was determined for the well known and largely used dye Coumarin 153, dissolved in 1-chloropropane. The Kennard-Stepanov relation connecting the absorption and emission spectra was used to check for the presence of more than one absorbing/emitting species and to investigate whether intramolecular vibrational redistribution completes in the C153 excited S ₁ state before the emission takes place. The emission spectrum corresponding to S ₁→S ₀ transition, was fitted at each temperature to the model function including the information on the dye vibrational modes coupling. In this way the displacement in equilibrium distance for the most active vibrational mode was determined for C153 in S ₁ and in S ₀. Using the temperature dependence of the fluorescence decay time and quantum yield, the non-radiative deactivation rate was determined. Its temperature dependence was compared to that calculated using the theoretical model with the most active vibrational mode displacement values taken from steady-state spectra analysis. The somewhat surprising dependence of the fluorescence decay time and quantum yield on temperature was related to non-trivial coupling between low-frequency vibrational modes of C153 in the excited and ground states.     

Vibronic properties of the F+ centre in strontium oxide

The shape and moments of the F⁺ absorption band in SrO have been measured between 4.2K and 300K. Analysis of the moments gives the effective frequency of the vibrational modes interacting with the centre as $\text{h}\text{?}\text{ω = 236 ± 20 cm}{}^{-1}$, and the Huang-Rhys factors for cubic and non-cubic modes as S_C = 3 ± 1 and S_NC = 4 ± 1 respectively.