Electronic states of the CeO molecule: Absorption,emission, and laser spectroscopy

The electronic spectrum of the CeO molecule is characterized by the existence of many 0-0 bands resulting from transitions between various Ω components of excited states and the 16 lower Ω states which arise from the lowest configuration… (4f)(6s). Classical studies of rotational structure of absorption and emission spectra have been extended, and argon-ion and tunable dye (coumarin 460, rhodamine 6G, rhodamine 101) lasers have been used to excite known transitions in bands which had previously been rotationally analyzed. The resulting fluorescence spectra have been used to establish the relative energies of the lower states. By tuning the lasers to excite analyzed transitions from different known electronic states it has been possible to determine the energies of 16 low-lying states, to assign quantum numbers to 14 with certainty, and to suggest assignments for the other 2. The resulting energy level diagram of lower states is discussed and shown to correlate well with the 4f6s configuration of the Ce²⁺ ion. From the energies of the low-lying states, those of the higher excited states are calculated and in some cases new values of vibrational and rotational constants are derived.     

Identification of excited singlet states of chlorophenol isomers

The UV spectra of optical absorption of para-, meta-, and ortho-chlorophenol are recorded in the gas phase. The bands of UV spectra are assigned to the electronic transitions of molecules to definite excited singlet states on the basis of calculations by the TDDFT B3LYP/6-311++G(d, p) method. In each case the electron configuration making the predominant contribution to the particular singlet state is determined. The energies of singlet electronic transitions are shown to depend on the energy spacing between the molecular orbitals involved in these transitions.     

Using two-dimensional photon echo spectroscopy to probe the fine structure of the ground state biexciton of CdSe nanocrystals

The origin of the fine structure of the ground state single- and biexciton of CdSe nanocrystals is reviewed, along with the theoretical framework used to describe these states. Calculations were performed to determine the transition dipole moments of optically allowed transitions from the single- to biexciton fine structure states. Two-dimensional photon echo spectroscopy measurements for a sample of CdSe nanocrystals are reported. The two-dimensional electronic spectrum at a population time of 0 fs is analyzed using a simulation based on k.p theory predictions of the exciton and biexciton manifolds of states. The analysis suggests that a particular excited state absorption transition from the single- to biexciton fine structure dominates the 2D spectra. These excited state absorptions are clearly resolved in 2D spectra and the method therefore has promise for gaining clearer insights into quantum dot spectroscopy.     

The laser-induced fluorescence spectrum of the 1,2,3-trifluorobenzene radical cation

Laser-induced fluorescence spectra of the radical cation of 1,2,3-trifluorobenzene have determined the origin of the electronic transition and the lifetime of the excited state in both the gas phase and solid Ne matrices. The gas phase spectrum shows relatively poorly resolved vibrational structure, as the lines seem to be badly broadened by rotational contours. The matrix spectra show extensive, well-resolved vibrational structure with small but noticeable matrix perturbations. The structure is also rather irregular and differs considerably between the ground and excited states. All of these observations are consistent with a considerable change in geometry between the two electronic states.     

Electronic Raman scattering and infrared absorption by arsenic acceptors in ZnTe

We have measured electronic Raman scattering spectra and infrared absorption spectra of arsenic doped ZnTe. Electronic transitions from the ground state to the excited states in the arsenic acceptor and also vibronic transitions accompanying 1 LO phonon have been observed in both spectra. Experimentally determined acceptor levels are compared with the theoretical calculation.     

Laser study of the photophysical properties of UF6

The purpose of this paper is to review the most relevant theoretical and experimental results reported in recent years, on the photophysical properties of the uranium hexafluoride molecule in the gas phase. Details of the structure of the molecular orbitals of UF₆ are discussed with reference to theoretical calculations of the electronic states. Tentative assignments of the electronic transitions in the experimental visible-uv absorption spectrum are also considered. The fluorescence properties of the excited states of UF₆ are critically reviewed. The use of laser beams to excite the fluorescence emission of UF₆ is shown to be a fruitful experimental technique. The measurement of fluorescence parameters (i.e. the emission and excitation spectra, the decay time and quantum yield) is a particularly valuable and sensitive way of studying the dynamics and structure of the excited electronic states. The different mechanisms of fluorescence quenching that have been proposed are also critically reviewed.     

Laser study of the photophysical properties of UF6

The purpose of this paper is to review the most relevant theoretical and experimental results reported in recent years, on the photophysical properties of the uranium hexafluoride molecule in the gas phase. Details of the structure of the molecular orbitals of UF₆ are discussed with reference to theoretical calculations of the electronic states. Tentative assignments of the electronic transitions in the experimental visible-uv absorption spectrum are also considered. The fluorescence properties of the excited states of UF₆ are critically reviewed. The use of laser beams to excite the fluorescence emission of UF₆ is shown to be a fruitful experimental technique. The measurement of fluorescence parameters (i.e. the emission and excitation spectra, the decay time and quantum yield) is a particularly valuable and sensitive way of studying the dynamics and structure of the excited electronic states. The different mechanisms of fluorescence quenching that have been proposed are also critically reviewed.     

Excited state quantum phase transitions in many-body systems

Phenomena analogous to ground state quantum phase transitions have recently been noted to occur among states throughout the excitation spectra of certain many-body models. These excited state phase transitions are manifested as simultaneous singularities in the eigenvalue spectrum (including the gap or level density), order parameters, and wave function properties. In this article, the characteristics of excited state quantum phase transitions are investigated. The finite-size scaling behavior is determined at the mean-field level. It is found that excited state quantum phase transitions are universal to two-level bosonic and fermionic models with pairing interactions.     

Quantum-chemical study of relation of spectral and luminescent properties of positively solvatochromic malononitrile-based merocyanine dyes with their structure

The electronic structure, the spectra, and the efficiency of photophysical processes of energy deactivation are calculated by a semiempirical method for three positively solvatochromic merocyanine dyes with different polymethine chain lengths. The electronic structure and spectra calculated by different modifications of the INDO method at different molecular geometries are compared, and the optimum geometry of the isolated molecule is chosen. The absorption spectra of dyes are interpreted, including the short-wave-length bands related to transitions to highest excited states. The possibility of a specific electrophilic solvation of these compounds in the ground and fluorescent states, as well as the contribution of specific intermolecular interactions to the total interaction with the medium, is estimated. The role played by the trans-cis isomerization of isolated merocyanine molecules in the deactivation of their excited states is considered.     

High-Resolution, Rotationally Resolved Electronic Spectroscopy of the MgNC Radical

High-resolution, rotationally resolved, laser-induced fluorescence (LIF) spectra for the origin band, as well as several transitions involving vibrationally excited levels of the ?2Pi <-- &Xtilde2Sigma+ electronic transition of the MgNC radical, have been recorded using the output of a pulse-amplified Ti:Sapphire ring laser. The MgNC radical was generated in a supersonic free jet expansion by simultaneous laser ablation of a magnesium rod and photolysis of acetonitrile (CH3CN). Rotational analysis yielded molecular constants for both the ground and excited states of the studied vibronic transitions. The molecular constants for the vibrationless state of the &Xtilde state are in excellent agreement with previous microwave studies of MgNC. Since the ? electronic state of MgNC is a linear 2Pi state, the bending vibronic level structure is subject to both Renner-Teller and spin-orbit coupling. Suggested vibronic assignments of the observed transitions, made considering both these interactions and with the aid of the rotational analysis, are discussed. Copyright 1999 Academic Press.