Search results for "Vibronic spectroscopy"
showing 10 items of 12 documents
Absorption spectrum of the and electronic transitions of ReF6
1999
Abstract The absorption spectra of the near-infrared and ultraviolet bands of ReF6 have been recorded with a commercial spectrophotometer. The vibronic assignments previously published by different authors are critically revised. A non-perturbative method has been used to calculate the linear Jahn–Teller levels for the ν5 mode in the ground electronic state. Some new vibronic parameter values are derived. The ν5 linear Jahn–Teller parameter in the X G′ g electronic state is found to be D5=0.103(9). The ultraviolet absorption spectrum has enabled us to determine relatively accurate values of the crystal-field (10Dq) and spin-orbit (ζd) parameters.
The temperature dependence of vibronic lineshapes: linear electron-phonon coupling.
2014
We calculate the effect of a linear electron-phonon coupling on vibronic transitions of dye molecules of arbitrary complexity. With the assumption of known vibronic frequencies (for instance from quantum-chemical calculations), we give expressions for the absorption or emission lineshapes in a second-order cumulant expansion. We show that the results coincide with those obtained from generalized Redfield theory if one uses the time-local version of the theory and applies the secular approximation. Furthermore, the theory allows to go beyond the Huang-Rhys approximation and can be used to incorporate Dushinsky effects in the treatment of the temperature dependence of optical spectra. We cons…
Single Molecule Studies of a Ladder Type Conjugated Polymer: Vibronic Spectra, Line Widths, and Energy Transfer
2014
Confocal fluorescence microscopy and spectroscopy are employed to investigate single poly(ladder-type pentaphenylene) (LPPentP) molecules dispersed in thin poly(methyl methacrylate) (PMMA) films at 1.2 K. Emission spectra of single chains show single as well as multi-chromophore emission indicating variegated communication along the chains. The vibronic structure in the emission spectra resembles the one found for other ladder-type polymers. Purely electronic zero-phonon lines in emission are substantially broadened, most probably due to fast spectral diffusion. By surmounting the limitations of emission spectroscopy, nonemitting donor chromophores, which transfer their excitation energy in…
The algebra eigenstates method for some systems with spin-like interactions
2006
International audience; An extension of the algebra eigenstates formalism is proposed to solve the eigenvalue equation for a class of problems involving "spin interactions". The method is detailed for the harmonic oscillator, su(2) and su(1, 1) algebras. Special emphasis is given to the resolution of problems in vibronic spectroscopy involving doubly degenerate electronic states.
Localization vs. Delocalization in Molecules and Clusters: Electronic and Vibronic Interactions in Mixed Valence Systems
1996
The interplay between electron delocalization and magnetic interactions play a key role in areas as diverse as solid state chemistry (bulk magnetic materials, superconductors,...) [1] and biology (iron-sulfur proteins, manganese-oxo clusters ...) [2]. In molecular inorganic chemistry these two electronic processes have been traditionally studied independently. Thus, the electron dynamics has been extensively investigated in mixedvalence dimers [3] as exemplified by the Creutz-Taube complex [(NH3)5RuII(pyrazine)RuIII(NH3)5]. In this kind of molecular complexes one extra electron is delocalized over two diamagnetic metal sites. Therefore, they constitute model systems for the study of the ele…
Spectroscopy of Hexafluorides with an Odd Number of Electrons: The Vibronic Bands of IrF6
1996
Abstract The low resolution absorption spectroscopy of the first five excited electronic states of IrF 6 has made possible some new assignments for the vibronic transitions of this molecule, and the determination of new vibronic parameter values. They are more accurate than those found in the literature. In this aim, we introduce a simplified tensorial formulation for the linear Jahn–Teller terms in a fourfold degenerate electronic state of an XY 6 -type molecule, which allows easier computation of matrix elements and avoids the use of perturbation theory. Methods for IrF 6 synthesis (using a dynamical flow system) and purification are also presented.
The importance of vibronic perturbations in ferrocytochrome c spectra: a reevaluation of spectral properties based on low-temperature optical absorpt…
2005
We have measured and analyzed the low-temperature (T=10 K) absorption spectrum of reduced horse heart and yeast cytochrome c. Both spectra show split and asymmetric Q(0) and Q(upsilon) bands. The spectra were first decomposed into the individual split vibronic sidebands assignable to B(1g) (nu15) and A(2g) (nu19, nu21, and nu22) Herzberg-Teller active modes due to their strong intensity in resonance Raman spectra acquired with Q(0) and Q(upsilon) excitations. The measured band splittings and asymmetries cannot be rationalized solely in terms of electronic perturbations of the heme macrocycle. On the contrary, they clearly point to the importance of considering not only electronic perturbati…
Mixed-Valence Molecular Unit for Quantum Cellular Automata: Beyond the Born-Oppenheimer Paradigm through the Symmetry-Assisted Vibronic Approach.
2016
In this article, we focus on the electron-vibrational problem of the tetrameric mixed-valence (MV) complexes proposed for implementation as four-dot molecular quantum cellular automata (mQCA).1 Although the adiabatic approximation explored in ref 2 is an appropriate tool for the qualitative analysis of the basic characteristics of mQCA, like vibronic trapping of the electrons encoding binary information and cell-cell response, it loses its accuracy providing moderate vibronic coupling and fails in the description of the discrete pattern of the vibronic levels. Therefore, a precise solution of the quantum-mechanical vibronic problem is of primary importance for the evaluation of the shapes o…
Mixed-valence polyoxometalate clusters. III. Vibronic problem for the 2-electron reduced heteropoly blue with the Keggin structure
1995
Abstract A general approach to the vibronic problem of delocalized electronic pairs in mixed-valence compounds is developed and applied to understand the ways of electron delocalization in dodecanuclear polyoxometalate clusters containing two moving electrons. The interplay between electronic and vibronic interactions is examined. The electronic spectrum is shown to consist of two spin triplets 3 T 1 and 3 T 2 and three spin singlets 1 A 1 , 1 E and 1 T 2 levels determined by the double-transfer processes (parameter P ). Jahn-Teller and pseudo-Jahn-Teller problems ( 3 T 1 + 3 T 2 ) ⊗ ( e + t 2 ) and ( 1 A 1 + 1 E + 1 T 2 ) ⊗ ( e + t 2 ) have been considered in the framework of the Piepho-Kr…
The lineshape of the electronic spectrum of the green fluorescent protein chromophore, part I: gas phase.
2014
The vibronic spectra of the green fluorescent protein chromophore analogues p-hydroxybenzylidene-2,3-dimethylimidazolinone (HBDI) and 3,5-tert-butyl-HBDI (35Bu) are similar in the vacuum, but very different in water or ethanol. To understand this difference, we have computed the vibrationally resolved solution spectra of these chromophores, using the polarizable continuum model (PCM) to account for solvent effects on the (harmonic) potential energy surfaces (PES). In agreement with experiment, we found that the vibrational progression increases with the polarity of the solvent, but we could neither reproduce the broadening, nor the large difference between the absorption spectra of HBDI and…