RESUMO
The vertical excitation and emission energies of the cytosine oxo-amino form were calculated at the TD DFT level of theory with several functionals, basis sets, and solvents with different polarity (PCM). They were compared with the experimental UV absorption and fluorescence maxima, revealing that the minimal deviation of the vertical excitation energies from the of UV absorption maxima can be achieved when the hybrid functional B3LYP is applied within the calculations. Regular correlations like curves with saturation between the vertical excitation/emission energies and the dielectric constants were registered. The relaxation of the 1ππ* excited state through an ethylene-like conical intersection S0/S1 should occur through decrease of the decay rate (commented qualitatively here) with the rise of the solvent polarity.
Assuntos
Citosina , Teoria da Densidade Funcional , Fluorescência , SolventesRESUMO
We performed a theoretical and experimental study of the (photo)stability of 3,5-dinitrocatechol (DNC) and its complexes with W(VI) and V(V). The investigation showed that irradiation of DNC is accompanied by a parallel proton migration from the hydroxy group to the neighboring NO2 group, which results in a large Stokes shift of the absorption and emission bands. It was found that W(VI) forms a more stable 1:2 complex than V(V). The complex is stable even under UV irradiation. The most stable W(VI)(DNC)2 conformer is comprised of two mutually perpendicular DNC molecules as ligands.
RESUMO
Using resonance-enhanced two-photon ionization spectroscopy with mass resolution of jet-cooled molecules, a low-resolution S(1) â S(0) vibronic spectrum of pseudoephedrine was recorded at the mass channels of three distinct fragments with m/z = 58, 71, and 85. Two of the fragments, with m/z = 71 and 85, are observed for the first time for this molecule. The vibronic spectra recorded at different mass channels feature different patterns, implying that they originate from different conformers in the cold molecular beam, following conformer-specific fragmentation pathways. Highly resolved spectra of all prominent vibronic features were measured, and from their analysis based on genetic algorithms, the molecular parameters of the conformers giving rise to the respective bands have been determined. Comparing the experimental results with those obtained from high-level ab initio quantum chemistry calculations, the observed prominent vibronic bands have been assigned to originate from four distinct conformers. The conformers are separated into two groups that have different fragmentation pathways determined by the different intramolecular interactions.
Assuntos
Broncodilatadores/química , Físico-Química , Pseudoefedrina/química , Íons/química , Cinética , Modelos Moleculares , Conformação Molecular , Espectroscopia Fotoeletrônica , Espectrofotometria Ultravioleta , Estereoisomerismo , Termodinâmica , VibraçãoRESUMO
The vibrational structure of the ionic ground state of different conformers of the biologically relevant molecule 2-phenylethanol has been investigated by combination of two-photon two-color mass-analyzed threshold ionization spectroscopy (MATI) and quantum chemical calculations at M05, MP2, and coupled cluster (CC) levels of theory with extended basis sets. MATI spectra recorded via gauche vibronic bands are with poor structure and increasing background, whereas the ones measured via vibronic bands of the anti conformers feature well-resolved vibronic structure in the cation. Ab initio computations predict three stable conformers for the 2-phenylethanol cation out of five initial neutral structures. None of the theoretical structures in the cation features a nonclassical OH...pi hydrogen bond in conjunction with the analysis of the MATI spectra. This provides clear evidence that the OH...pi hydrogen bond stabilizing the lowest-energy gauche conformer in the neutral breaks upon ionization.
