Search results for "excited state"
showing 10 items of 1387 documents
Alkali Blues: Blue‐Emissive Alkali Metal Pyrrolates
2019
2-Iminopyrroles [HtBu L, 4-tert-butyl phenyl(pyrrol-2-ylmethylene)amine] are non-fluorescent π systems. However, they display blue fluorescence after deprotonation with alkali metal bases in the solid state and in solution at room temperature. In the solid state, the alkali metal 2-imino pyrrolates, M(tBu L), aggregate to dimers, [M(tBu L)(NCR)]2 (M=Li, R=CH3 , CH(CH3 )CNH2 ), or polymers, [M(tBu L)]n (M=Na, K). In solution (solv=CH3 CN, DMSO, THF, and toluene), solvated, uncharged monomeric species M(tBu L)(solv)m with N,N'-chelated alkali metal ions are present. Due to the electron-rich pyrrolate and the electron-poor arylimino moiety, the M(tBu L) chromophore possesses a low-energy intra…
Cobaltocenium substituents as electron acceptors in photosynthetic model dyads
2017
Abstract Cobaltocenium carboxylic acid hexafluorophosphate has been attached to a zinc(II) meso-tetraphenyl porphyrin chromophore via an amide linkage. Optical and electrochemical studies reveal that the metallocene and the porphyrin interact only negligibly in the ground state of the dyad. Photoinduced charge-shift from the zinc porphyrin to the cobaltocenium substituent to give the zinc porphyrin radical cation and the cobaltocene occurs upon exciting the porphyrin with light. Steady state emission, time-resolved fluorescence and transient absorption pump–probe spectroscopy in addition to density functional theory calculations suggest that the charge shift to the cobaltocenium substituent…
Photo-Chromium: Sensitizer for Visible-Light-Induced Oxidative C−H Bond Functionalization-Electron or Energy Transfer?
2017
The chromium(III) sensitizer [Cr(ddpd)2]3+ - based on an earth-abundant metal center - possesses a unique excited state potential energy landscape (ddpd = N,N'-dimethyl-N,N'-dipyridine-2-ylpyridine-2,6-diamine). The very large energy gap between the redox active and substitutionally labile 4T2 state and the long-lived low-energy 2E spin-flip state enables a selective, efficient sensitization of triplet dioxygen to give singlet dioxygen. Ultrafast intersystem crossing after the Franck Condon point from the 4T2 to the 2E excited state within 3.5 ps precludes intermolecular electron transfer pathways from the ultrashort-lived excited 4T2 state. This specific excited state reactivity enables a …
The high overtone and combination levels of SF6 revisited at Doppler-limited resolution: A global effective rovibrational model for highly excited vi…
2017
Abstract Sulfur hexafluoride is an important prototypal molecule for modeling highly excited vibrational energy flow and multi quanta absorption processes in hexafluoride molecules of technological importance. It is also a strong greenhouse gas of anthropogenic origin. This heavy species, however, features many hot bands at room temperature (at which only 30% of the molecules lie in the ground vibrational state), especially those originating from the lowest, v 6 =1 vibrational state. Using a cryogenic long path cell with variable optical path length and temperatures regulated between 120 and 163 K, coupled to Synchrotron Radiation and a high resolution interferometer, Doppler-limited spectr…
Mechanism of the OH Radical Addition to Adenine from Quantum-Chemistry Determinations of Reaction Paths and Spectroscopic Tracking of the Intermediat…
2016
The OH radical is a well-known mediator in the oxidation of biological structures like DNA. Over the past decades, the precise events taking place after reaction of DNA nucleobases with OH radical have been widely investigated by the scientific community. Thirty years after the proposal of the main routes for the reaction of •OH with adenine (Vieira, A.; Steenken, S. J. Am. Chem. Soc. 1990, 112, 6986−6994), the present work demonstrates that the OH radical addition to C4 position is a minor pathway. Instead, the dehydration process is mediated by the A5OH adduct. Conclusions are based on density functional theory calculations for the ground-state reactivity and highly accurate multiconfigur…
Fluorescence Probes Exhibit Photoinduced Structural Planarization: Sensing In Vitro and In Vivo Microscopic Dynamics of Viscosity Free from Polarity …
2020
We demonstrate the construction of wavelength λ-ratiometric images that allow visualizing the distribution of microscopic dynamics within living cells and tissues by using the newly developed principle of fluorescence response. The bent-to-planar motion in the excited state of incorporated fluorescence probes leads to elongation of the π-delocalization, resulting in microviscosity-dependent but polarity-insensitive interplay between well-separated blue and red bands in emission spectra. This allows constructing the exceptionally contrasted images of cellular dynamics. Moreover, the application of probes with increased affinity toward biological membranes allowed detecting the differences in…
Studies towards a directional polychromatic sodium laser guide star
2018
In this work we discuss a mechanism for generation of a coherent source of light from the mesosphere as a new concept of directional laser guide star. In contrast to the near-isotropic spontaneous emission, nonlinear processes in atomic vapors like amplified spontaneous emission can yield highly directional emission in the forward and backward directions. Along with directional emission, excited sodium atoms also radiate at different wavelength creating a polychromatic laser guide star (PLGS). If feasible, a directional PLGS would provide a net gain in the return flux of several orders of magnitude compared to traditional LGS schemes, making possible laser-guided tip/tilt-correction in adap…
Parametrical Optomechanical Oscillations in PhoXonic Whispering Gallery Mode Resonators
2019
AbstractWe report on the experimental and theoretical analysis of parametrical optomechanical oscillations in hollow spherical phoxonic whispering gallery mode resonators due to radiation pressure. The optically excited acoustic eigenmodes of the phoxonic cavity oscillate regeneratively leading to parametric oscillation instabilities.
Lifetimes of core-excited states in semi-magic $^{95}$Rh
2020
Lifetimes of negative-parity states have been determined in the neutron deficient semi-magic (N = 50) nucleus 95Rh. The fusion-evaporation reaction 58Ni(40Ca,3p) was used to populate high-spin states in 95Rh at the Grand Accélérateur National d’Ions Lourds (GANIL) accelerator facility. The results were obtained using the Doppler Shift Attenuation Method (DSAM) based on the Doppler broadened line shapes produced during the slowing down process of the residual nuclei in a thick 6mg/cm2 metallic target. B(M1) and B(E2) reduced transition strengths are compared with predictions from large-scale shell-model calculations. peerReviewed
Isomeric state of $^{80}$Y and its role in the astrophysical rp-process
2001
5 pages, 7 figures.-- PACS nrs: 21.10.Tg; 23.20.Nx; 27.50.+e.