Far infrared electronic and vibronic transitions of Nd super 3 super plus in the tysonite lanthanide fluorides.
Far IR electronic and vibronic transitions in single crystals of Nd ions in tysonite lanthanide fluorides
Lowndes, R. P.↗
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Vibronic Transitions of Hexagonal Rare-Earth Trichlorides. I
Phonon spectrum of neodymium trichloride crystal lattice determined from polarized vibronic transition spectra and Zeeman effect of trivalent Pr and Nd impurity ions
VIBRATIONAL SPECTRUM↗
Vibronic transitions of hexagonal rare-earth trichlorides. II.
Absorption spectra of rare earth trichlorides with trivalent Pr, observing vibronic transitions noting assignments of phonon branches
LATTICE VIBRATION↗
Analysis of vibronic transitions in titanium doped sapphire using the temperature of the fluorescence spectra
An analysis of the fluorescence spectra of titanium-doped sapphire crystals for temperatures ranging from 13 to 578 K is made. Zero- and multiphoton assisted electronic transitions are observed at temperatures below 125 K. Zero-phonon transition energies agree with previously reported measured and predicted values. Photon-assisted transitions suggest that two principle modes of lattice vibrations with energies of 220 and 260/cm are coupled to the electronic 2T2g state. A single phonon energy of 173/cm is observed to couple to the 2Eg electronic state. Crossover energy is estimated to be about 11,800/cm using a simple harmonic approximation. Lineshape analysis is performed. The fluorescence lifetime as measured to be a constant 3.9 microsec below 150 k decreasing to 2.9 microsec at 300 K.
Byvik, C. E.↗
Cavity Ring Down Spectroscopy of Cold Neutral Phenanthrene and Phenanthridine in Supersonic Jets
Here we study the effect of nitrogen insertion on the electronic spectra of polycyclic aromatic hydrocarbon (PAH) molecules measured under laboratory conditions that are relevant for comparison with astronomical data. We examine the case of the substitution of carbon atoms by nitrogen atoms in the benzenoid skeleton of phenanthrene (C 14 H 10 ), a prototype non-compact PAH. The vibronic transitions of the 2 1 A 1 (S 1 )←X 1 A 1 (S 0 ) electronic absorption band system of neutral phenanthrene (C 14 H 10 ) and phenanthridine (C 13 H 9 N) molecules seeded in a supersonic free jet expansion of argon gas are measured in the 315-345 nm region using the cavity ring down spectroscopy (CRDS) technique. Additional measurements of the absorption spectra of the phenanthrene, phenanthridine, and 1,10-phenanthroline (C 12 H 8 N 2 ) molecules isolated in 10-K solid argon matrices are also presented. The results obtained confirm that laboratory spectra of cold, isolated molecules obtained under astrophysically relevant conditions are required for a direct, unambiguous comparison with astronomical observations as well as for the understanding of the physical evolution of the interstellar medium.
Absorption band↗
IR pumped third-harmonic generation and sum-frequency generation in diatomic molecules
The potential efficiency of using nonlinear up-conversion techniques for the high efficiency type lasers (CO,CO2, and chemical) is assessed. Results indicate that: the small pump photon energy necessitates the use of molecular media for conversion if resonance enhancement is to be used and that molecular systems present several problems. These difficulties include: their levels are complex; their transition probabilities are often unknown; and the oscillator strengths among vibrational levels in the ground electronic state of a molecule are much smaller than those among electronic states of an atom, thus limiting the magnitude of nonlinear interactions. It is shown that this problem can be eliminated by making use of vibronic transitions which, being primarily electronic transitions have much larger matrix elements and efficient conversion can be achieved with molecular systems.
She, C. Y.↗
Infrared-pumped third-harmonic and sum-frequency generation in diatomic molecules
Using molecular hydrogen as a model system, we present a calculation which demonstrates the feasibility of efficient third-harmonic and sum-frequency generation of IR laser radiation by diatomic molecular gases. A conversion efficiency of 10% without phase matching is achievable with a modest laser intensity of about 20 MW/sq cm. In addition to a two-photon resonance, the efficient conversion depends on a mechanism which makes use of virtual vibronic transitions exclusively. Possible methods for phase matching are also suggested.
She, C. Y.↗
Two-photon excitation of nitric oxide fluorescence as a temperature indicator in unsteady gas-dynamic processes
A laser induced fluorescence technique, suitable for measuring fluctuating temperatures in cold turbulent flows containing very low concentrations of nitric oxide is described. Temperatures below 300 K may be resolved with signal to noise ratios greater than 50 to 1 using high peak power, tunable dye lasers. The method relies on the two photon excitation of selected ro-vibronic transitions. The analysis includes the effects of fluorescence quenching and shows the technique to be effective at all densities below ambient. Signal to noise ratio estimates are based on a preliminary measurement of the two photon absorptivity for a selected rotational transition in the NO gamma (0,0) band.
Mckenzie, R. L.↗
Single-pulse gas thermometry at low temperatures using two-photon laser-induced fluorescence in NO/N2 mixtures
A technique suitable for measuring fluctuating temperatures in supersonic turbulent flows of N2 seeded with NO has been demonstrated in a nonflowing cell. The method relies on the two photon excitation of two selected ro-vibronic transitions in the NO gamma (alpha 2 sigma+, v prime = 0 yields ch1zp1, v double prime = 0).
Gross, K. P.↗
Single-pulse gas thermometry at low temperatures using two-photon laser-induced fluorescence in NO-N2 mixtures
A technique suitable for measuring fluctuating temperatures in supersonic turbulent flows of N2 seeded with NO has been demonstrated in a nonflowing cell. The method relies on the two photon excitation of two selected ro-vibronic transitions in the NO gamma (alpha 2 sigma+, v prime = 0 yields ch1zp1, v double prime = 0). Previously announced in STAR as N83-20079
Gross, K. P.↗
On a vibronic origin for the diffuse band spectrum
Duley (1982) has proposed that many of the diffuse interstellar bands in the wavelength interval 542-677 nm arise from vibronic transitions of Cr (3+) ions in MgO grains. No explanation has been offered for the fact that as many as 85 of the possible 108 transitions of this system have not been observed in the interstellar medium. Moreover, the relative intensities of the diffuse bands which are observed appear to be inconsistent with their assignment. It is therefore concluded that this model is not consistent with the observations.
Nuth, J. A.↗
Remarks on a vibronic origin for the diffuse band spectrum
It has been demonstrated that the diffuse band spectrum could not originate as a series of vibronic transitions from atomic impurities in interstellar MgO grains as has recently been proposed since laboratory spectra of such materials show no evidence for such complex structure. Furthermore, recent observational evidence indicates that the extinction feature at 160 nm in the standard interstellar extinction curve upon which the identification of interstellar MgO was founded is actually the result of a calibration error in the original observational data.
Nuth, J. A.↗
Induced ClO vacuum ultraviolet fluorescence
Some vibronic transitions of ClO such as G(v-prime = 11 )-X(v-double prime = 10), G(v-prime = 5)-X(v-double prime = 3) and H(v-prime = 4)-X(v-double prime = 2), which promote overtones of X(2pi3/2) to bound Rydberg states, are nearly resonant with the 130.6 nm O-atom emission line and possess sizable Franck-Condon factors. On this basis broadband detection of 'O atom' fluorescence in experiments involving vibrationally excited ClO(X) is ascribed to the radiative decay of ClO(G, H) rather than to the formation of O atoms; these observations raise the probability of monitoring ClO(X; v = 0) by VUV-induced fluorescence.
Colussi, A. J.↗
Porphyrins in the interstellar medium (in grains)
Spectral sensitivity of the chromophores to their immediate chemical environment establishes some of the chemical constituents of the grains in which they reside. These are: (1) Paraffins, such as, octane, nonane, decane, and others...(needed for Shpolskii matrices and producing quasilines); and (2) Pyridine. The presence of pyridine is required not only to produce the spectral DIB matching, but also to produce the 36 cm(sup -1) crystal field splitting of the S(sub 1) electronic state. The presence of pyridine in the grains can be confirmed spectroscopically. Pyridine produces a transmission window at 2175 A, matching exactly the well known UV hump. On grain reflection, some of the incoming UV radiation is absorbed into the grain's outer layers. Spikes in the lab and in the astronomical data are due to vibronic transitions in pyridine. The lab spectroscopy reported here clearly establishes the presence of MgTBP, H2TPB, and pyridine in the interstellar grains. The high fluorescence efficiency of MgTBP (being optically pumped in the visible) apparently accounts for all the observed UIR emissions.
Johnson, Fred M.↗
Electronic spectroscopy of PAHs and PAH derivatives in supersonic jet
Polycyclic Aromatic Hydrocarbon (PAHs) molecules are attracting much attention in the astrophysical and astrochemical communities because of their ubiquitous presence in space due to their ability to survive in the harsh environmental conditions of the interstellar medium(ISM). The objective of this work is to provide gas phase, high-resolution spectroscopic data on the electronic and vibronic transitions of PAHs and their nitrogenated derivatives measured in astrophysically relevant conditions.
CRDS↗
Observation of a two-vibron bound-to-unbound transition in solid deuterium at high pressure
We have observed a two-vibron bound-to-unbound transition in solid D2 by Raman scattering at a pressure of 34(2) GPa. We investigated the transition by increasing the vibron bandwidth, through the application of pressure, until it dominated the intramolecular anharmonicity. We present an analysis of a simple Hamiltonian that gives the experimental bivibron binding energy and the critical bandwidth-to-anharmonicity ratio. Our results indicate that while the vibron bandwidth increases markedly with pressure, the anharmonicity remains constant.
Eggert, Jon H.↗
Computational Spectroscopy of Polycyclic Aromatic Hydrocarbons In Support of Laboratory Astrophysics
Polycyclic aromatic hydrocarbons (PAHs) are strong candidates for the molecular carriers of the unidentified infrared bands (UIR) and the diffuse interstellar bands (DIBs). In order to test the PAH hypothesis, we have systematically measured the vibronic spectra of a number of jet-cooled neutral and ionized PAHs in the near ultraviolet (UV) to visible spectral ranges using the cavity ring-down spectroscopy. To support this experimental effort, we have carried out theoretical studies of the spectra obtained in our measurements. Ab initio and (time-dependent) density.functiona1 theory calculations are performed to obtain the geometries, energetics, vibrational frequencies, transition dipole moments, and normal coordinates of these PAH molecules. Franck-Condon (FC) calculations and/or vibronic calculations are then performed using the calculated normal coordinates and vibrational frequencies to simulate the vibronic spectra. It is found that vibronic interactions in these conjugated pi electron systems are often strong enough to cause significant deviations from the Born-Oppenheimer (BO) approximation. For vibronic transitions that are well described by the BO approximation, the vibronic band profiles are simulated by calculating the rotational structure of the vibronic transitions. Vibronic oscillator strength factors are calculated in the frame of the FC approximation from the electronic transition dipole moments and the FC factors. This computational effort together with our experimental measurements provides, for the first time, powerful tools for comparison with space-based data and, hence, a powerful approach to understand the spectroscopy of interstellar PAH analogs and the nature of the UIR and DIBs.
Tan, Xiaofeng↗
On nuclear spin statistics in rotational transition intensities in tetrahedral AB4 molecules
A general expression is derived for the integrated intensity of rotational transitions in the vibronic ground state of tetrahedral molecules, taking into account the nuclear spin statistics. It is shown that the ratio of this expression to previously published spin-free integrated intensities depends only on the tensor character N of the operator driving the transition, the appropriate rotational quantum numbers J and J', and the nuclear spin of the identical nuclei. Tables are given for N = 3, 4 and J no more than 50, which enable the calculation of integrated intensities for octopole and hexadecapole collision-induced dipole-moment transitions, centrifugal-distortion-induced dipole-moment transitions, and centrifugal-distortion-induced anisotropic-polarizability-tensor Raman transitions.
Rosenberg, A.↗