Search results for "Ground state"
showing 10 items of 928 documents
Cooperative phenomena and light-induced bistability in iron(II) spin-crossover compounds
1999
In iron(II) spin-crossover compounds, the transition from the 1A1 low-spin state at low temperatures to the 5T2 high-spin state at elevated temperatures is accompanied by a large increase in metal-ligand bond lengths. The resulting elastic interactions may be pictured as an internal pressure which is proportional to the concentration of the low-spin species. Because pressure stabilises the low-spin state relative to the high-spin state this results in a positive feedback. Thermal transition curves in neat iron(II) spin-crossover compounds are thus invariable much steeper than in diluted mixed crystals, and the high-spin→low-spin relaxation following the light-induced population of the high-…
A combined theoretical and experimental determination of the electronic spectrum of acetone
1996
A combined ab initio and experimental investigation has been performed of the main features of the electronic spectrum of acetone. Vertical transition energies have been calculated from the ground to the ny→π∗, π→π∗, σ→π∗, and the n=3 Rydberg states. In addition, the 1A1 energy surfaces have been studied as functions of the CO bond length. The 1A1 3p and 3d states were found to be heavily perturbed by the π→π∗ state. Resonant multiphoton ionization and polarization‐selected photoacoustic spectra of acetone have been measured and observed transitions were assigned on internal criteria. The calculated vertical transition energies to the ny→π∗ and all Rydberg states were found to be in agreeme…
Ab initio study on the low-lying excited states of retinal
1997
Ab initio results for the electronic spectrum of all-trans-retinal and its truncated model 3-methyl-all-trans (10-s-cis)-2,4,6,8,10-undecapentaen-1-al are presented. The study includes geometry determination of the ground state. Vertical excitation energies have been computed using multiconfigurational second-order perturbation theory through the CASPT2 formalism. The lowest singlet excited state in gas phase is predicted to be of nπ∗ character. The lowest triplet state corresponds, however, to a ππ∗ state. The most intense feature of the spectrum is due to the strongly dipole-allowed ππ∗ transition, in accordance with the observed maximum in the one-photon spectra. The vertical excitation …
Light‐Induced On/Off Switching of the Surfactant Character of the o ‐Cobaltabis(dicarbollide) Anion with No Covalent Bond Alteration
2021
Cobaltabis(dicarbollide) anion ([o-COSAN]- ) is a well-known metallacarborane with multiple applications in a variety of fields. In aqueous solution, the cisoid rotamer is the most stable disposition in the ground state. The present work provides theoretical evidence on the possibility to photoinduce the rotation from the cisoid to the transoid rotamer, a conversion that can be reverted when the ground state is repopulated. The non-radiative decay mechanisms proposed in this work are coherent with the lack of fluorescence observed in 3D fluorescence mapping experiments performed on [o-COSAN]- and its derivatives. This phenomenon induced by light has the potential to destruct the vesicles an…
Photoluminescence activity in natural silica excited in the vacuum-UV range
1999
Abstract We report an experimental study on the optical absorption and photoluminescence detected in samples of natural silica. Our results show that the two emission bands, β (∼3.1 eV) and α E (∼4.3 eV), have an excitation profile in the vacuum ultraviolet region with a maximum at ∼7.5 eV. This excitation profile indicates that, in terms of energy levels of the luminescent defect, there is a transition from a ground state, S 0 , to a second excited state, S 2 , able to excite PL emission, in addition to the well known transition corresponding to the optical absorption band, B 2β . Our data are in a quantitative agreement with `ab initio' calculations carried out for a two-fold coordinated …
Isotope Effect on the Infrared Photoluminescence Decay of Interstitial Oxygen Molecules in Amorphous SiO2
2009
The decay constants of the a1Δg(v=0)→X3Σg-(v=0) infrared photoluminescence (PL) of isotopically-labeled oxygen molecules 16O18O and 18O2 dissolved in the interstitial voids of a-SiO2 are ~1.7 and ~2.5 times larger than that of 16O2. This difference originates from the isotope shift in the energy of the nonradiative transitions from the a state to the vibronic levels of the X ground state. Calibration of the PL quantum yield using the measured decay constants is essential to measure the correct concentration of isotopically-labeled interstitial O2.
Transient FTIR spectroscopy after one- and two-colour excitation on a highly luminescent chromium(III) complex.
2021
The development of photoactive transition metal complexes with Earth-abundant metals is a rapidly growing research field, where a deeper understanding of the underlying photophysical processes is of great importance. A multitude of potential applications in the fields of photosensitizing, optical sensing, photoluminescence and photoredox catalysis motivates demanding spectroscopic studies. We applied a series of high-level spectroscopic methods on the previously reported highly luminescent chromium(iii) complex [Cr(ddpd)2](BF4)3 (ddpd = N,N'-dimethyl-N,N'-dipyridine-2-ylpyridine-2,6-diamine) possessing two near-IR emissive doublet states with microsecond lifetimes. Luminescence measurements…
Optical properties of phosphorous-related point defects in silica fiber preforms
2009
Physical review / B 80, 205208 (2009). doi:10.1103/PhysRevB.80.205208
Modification of vacuum-ultraviolet absorption of SiOH groups in SiO2 glass with temperature, F2 laser irradiation, and H–D isotope exchange
2006
Abstract Variations of vacuum-ultraviolet (VUV) absorption of silanol (SiOH) groups in synthetic wet SiO 2 glass with temperature, exposure to F 2 laser light, and with H–D isotope exchange were examined at photon energies below 8 eV. The intensity of the VUV absorption band decreases with cooling or with exposure to F 2 laser light. The spectral changes in both cases are qualitatively similar and are attributed to an alternation of the bonding configuration of SiOH groups from isolated into hydrogen-bonded states. However, the resultant states are distinctly different: the hydrogen-bonded state formed on cooling is restored reversibly to the isolated state on heating, while that induced by…
Electronic Excitation Energy Transfer between Two Single Molecules Embedded in a Polymer Host
2007
Unidirectional electronic excitation energy transfer from a photoexcited donor chromophore to a ground state acceptor chromophore - both linked by a rigid bridge - has been investigated by low temperature high-resolution single molecule spectroscopy. Our approach allows for accurately accessing static disorder in the donor and acceptor electronic transitions and to calculate the spectral overlap for each couple. By plotting the experimentally determined transfer rates against the spectral overlap, we can distinguish and quantify Förster- and non-Förster-type contributions to the energy transfer.