Search results for "Electronic transition"
showing 10 items of 61 documents
Vibrational analysis of the electronic spectrum of ethylene based onab initio SCF-CI calculations
1972
Ab initio calculations for CH2 twisting and CC stretching vibrational wavefunctions and energy levels are reported for various electronic states of ethylene C2H4. Electronic transition moments between these states are also obtained to allow a calculation of the oscillator strengths for vibrational transitions involved in various electronic band systems; from this study it is concluded that thevertical electronic energy differenceΔE e may differ significantly from the energy of the absorption maximumΔE max with which it is often equated. In particular it is found in the case of theπ→π * singlet-singlet excitation of ethylene that theΔE e value overestimates the most probable vibrational tran…
Quantum chemical simulation of excited states of chlorophylls, bacteriochlorophylls and their complexes
2006
The present review describes the use of quantum chemical methods in estimation of structures and electronic transition energies of photosynthetic pigments in vacuum, in solution and imbedded in proteins. Monomeric Mg-porphyrins, chlorophylls and bacteriochlorophylls and their solvent 1:1 and 1:2 complexes were studied. Calculations were performed for Mg-porphyrin, Mg-chlorin, Mg-bacteriochlorin, mesochlorophyll a, chlorophylls a, b, c(1), c(2), c(3), d and bacteriochlorophylls a, b, c, d, e, f, g, h, plus several homologues. Geometries were optimised with PM3, PM3/CISD, PM5, ab initio HF (6-31G*/6-311G**) and density functional B3LYP (6-31G*/6-311G**) methods. Spectroscopic transition energ…
Ultrafast dynamics of halogens in rare gas solids
2007
We perform time resolved pump-probe spectroscopy on small halogen molecules ClF, Cl2, Br2, and I2 embedded in rare gas solids (RGS). We find that dissociation, angular depolarization, and the decoherence of the molecule is strongly influenced by the cage structure. The well ordered crystalline environment facilitates the modelling of the experimental angular distribution of the molecular axis after the collision with the rare gas cage. The observation of many subsequent vibrational wave packet oscillations allows the construction of anharmonic potentials and indicate a long vibrational coherence time. We control the vibrational wave packet revivals, thereby gaining information about the vib…
Spin-orbit coupling constants from coupled-cluster response theory
2000
A scheme for the calculation of spin-orbit coupling constants using coupled-cluster (CC) electronic structure methods is described based on response-theory expressions for transition properties. An implementation is reported for singlet–triplet transitions within the coupled-cluster singles and doubles (CCSD) approximation. An atomic mean-field representation of the spin-orbit interaction is used to simplify the calculation of spin-orbit coupling constants. Sample calculations are presented for spin-orbit couplings for the 11Σ+→13Π transitions for BH and AlH and for the 11A′→13A″ and the 13A″→11A″ transitions for the silylenes HSiX, X=F, Cl, Br, and are compared to results obtained from ful…
Enhanced nanoscopy of individual CsPbBr3 perovskite nanocrystals using dielectric sub-micrometric antennas
2020
We demonstrate an efficient, simple, and low-cost approach for enhanced nanoscopy in individual green emitting perovskite (CsPbBr3) nanocrystals via TiO2 dielectric nanoantenna. The observed three- to five-fold emission enhancement is attributed to near-field effects and emission steering promoted by the coupling between the perovskite nanocrystals and the dielectric sub-micrometric antennas. The dark-field scattering configuration is then exploited for surface-enhanced absorption measurements, showing a large increase in detection sensitivity, leading to the detection of individual nanocrystals. Due to the broadband spectral response of the Mie sub-micrometric antennas, the method can be e…
Heme symmetry, vibronic structure, and dynamics in heme proteins: ferrous nicotinate horse myoglobin and soybean leghemoglobin.
2000
We report the visible and Soret absorption bands, down to cryogenic temperatures, of the ferrous nicotinate adducts of native and deuteroheme reconstituted horse heart myoglobin in comparison with soybean leghemoglobin-a. The band profile in the visible region is analyzed in terms of vibronic coupling of the heme normal modes to the electronic transition in the framework of the Herzberg–Teller approximation. This theoretical approach makes use of the crude Born–Oppenheimer states and therefore neglects the mixing between electronic and vibrational coordinates; however, it takes into account the vibronic nature of the visible absorption bands and allows an estimate of the vibronic side bands…
Cyclooctadienine — hoch gespannte C 8 H 8 ‐Kohlenwasserstoffe
1985
Mit Hilfe der MNDO-Methode werden die energiearmsten Konformationen der vier strukturisomeren Cyclooctadienine 1–4 berechnet. Aus ihren Bildungswarmen ΔHf konnen durch Bezug zu den Cyclooctatrienen 5 und 6 die geometrischen Ringspannungen Eg abgeschatzt werden. Als experimentelle Sonde fur die Ringspannung dienen die UV-, IR (Raman)- und 13C-NMR-Spektren. Cyclooctadienynes — Highly Strained C8H8-Hydrocarbons Applying the MNDO-method the conformations with lowest energy of the isomeric cyclooctadienynes 1–4 are calculated. The geometrical ring strains Eg can be evaluated from the enthalpies of formation ΔHf in relation to the cyclooctatrienes 5 and 6. UV, IR (Raman) and 13C NMR spectra serve…
Isotope shifts and hyperfine structure in the transitions of stable calcium isotopes and calcium-41
1998
Isotope shifts and hyperfine structure in the 4s2 1S0 → 4s4p 1P1 and 4s2 1S0 → 4s4d 1D2 transitions of calcium have been measured with high-precision laser spectroscopy. Calcium atoms in an atomic beam were excited with single-frequency cw dye and titanium sapphire lasers and then photoionized with the 363.8 nm or 514.5 nm line of an argon ion laser. The resulting ions were analyzed and detected with a quadrupole mass spectrometer. Isotope shifts for all stable calcium isotopes and the radionuclide 41Ca have been measured in both transitions. The corresponding field shift and specific mass shift coefficients as well as hyperfine structure constants for the isotopes 41, 43Ca have been derive…
Combined Theoretical and Experimental Study of the Photophysics of Asulam
2013
The photophysics of the neutral molecular form of the herbicide asulam has been described in a joint experimental and theoretical, at the CASPT2 level, study. The unique π → π* aromatic electronic transition (f, ca. 0.5) shows a weak red-shift as the polarity of the solvent is increased, whereas the fluorescence band undergoes larger red-shifts. Solvatochromic data point to higher dipole moment in the excited state than in the ground state (μ(g)μ(e)). The observed increase in pKa in the excited state (pKa* - pKa, ca. 3) is consistent with the results of the Kamlet-Abboud-Taft and Catalán et al. multiparametric approaches. Fluorescence quantum yield varies with the solvent, higher in water (…
On the chemiluminescence emission of luminol: protic and aprotic solvents and encapsulation to improve the properties in aqueous solution.
2020
Luminol is a popular molecule that is currently gaining further interest due to its potential role for non-invasive cancer treatments. Design of more efficient derivatives in this context would benefit from a clear knowledge on the origin of the distinct intensity and spectroscopic properties in protic and aprotic solvents observed experimentally, which are still not rationalized. By efficiently combining molecular dynamics, quantum methodologies based on density functional theory and multiconfigurational quantum chemistry and hybrid approaches, and developing herein a computational approach for accurately determining "molar negative extinction (or gain) coefficients of emission", we firstl…