Search results for "EXCITATION"

Dipole moments of 4′-aminoflavonols determined using electro-optical absorption measurements or molecular Stark-effect spectroscopy

2002

The electro-optical absorption measurements (EOAM) were used to measure the dipole moments of the normal form of 4 � -(methoxy)-3hydroxyflavone (FOM), 4 � -(dimethylamino)-3-hydroxyflavone (FME), and 4 � -N-(15-azacrown-5)-3-hydroxyflavone (FCR). For these probes the excited state intramolecular proton transfer (ESIPT) takes place. For comparison, the dipole moments of 4 � -(dimethylamino)-3methoxyflavone (FME3ME), for which ESIPT is lacking, were measured. In the case of FCR, FME, and FME3ME the equilibrated ground (µg) and excited Franck–Condon state (µ FC ) electrical dipole moments are parallel to each other and also parallel to the transition dipole moment. The electrical dipole moment…

A comparison of excited state properties for iterative approximate triples linear response coupled cluster methods

2001

Abstract A computational study of the potential energy curves of the 1 Π state of BH, 1 Π state of CH + , 1 Σ u and 1 Π u states of C 2 , 1 Π state of CO, and 1 Π g and 1 Σ − u states of N 2 is carried out with the CC3 and CCSDT-3 corrections to EOMEE-CCSD. Good agreement in structure, vibrational frequencies, and excitation energies of these iterative triples-corrected methods with respect to experiment is found for most of these examples. However, deficiencies in the approximate treatment of triples is evident for BH and CH + .

Evidence for long-lived, optically generated quenchers of excitons in single-walled carbon nanotubes.

2011

The nonlinear dependence of near-infrared photoluminescence (PL) emission on excitation intensity has been measured for individual nanotubes representing six different (n,m) species. Significant deviations from linearity are observed for intensities as low as ~100 W/cm(2), and an approximate inverse correlation is found between nonlinearity and PL action cross section (brightness). A model in which all PL nonlinearity arises from exciton-exciton annihilation is insufficient to account for the experimental data using realistic parameters. It is proposed that additional nonlinear quenching arises from photoinduced quenching states or species with longer lifetimes than emissive excitons. Evide…

Deformation and mixing of coexisting shapes in neutron-deficient polonium isotopes

2015

Coulomb-excitation experiments are performed with postaccelerated beams of neutron-deficient Po196,198,200,202 isotopes at the REX-ISOLDE facility. A set of matrix elements, coupling the low-lying states in these isotopes, is extracted. In the two heaviest isotopes, Po200,202, the transitional and diagonal matrix elements of the 2+1 state are determined. In Po196,198 multistep Coulomb excitation is observed, populating the 4+1,0+2, and 2+2 states. The experimental results are compared to the results from the measurement of mean-square charge radii in polonium isotopes, confirming the onset of deformation from Po196 onwards. Three model descriptions are used to compare to the data. Calculati…

Tuning Azoheteroarene Photoswitch Performance through Heteroaryl Design

2017

International audience; Photoswitchable compounds, which can be reversibly switched between two isomers by light, continue to attract significant attention for a wide array of applications. Azoheteroarenes represent a relatively new but understudied type of photoswitch, where one of the aryl rings from the conventional azobenzene class has been replaced with a five-membered heteroaromatic ring. Initial studies have suggested the azoheteroarenes – the arylazopyrazoles in particular – to have excellent photoswitching properties (quantitative switching and long Z isomer half-life). Here we present a systematic computational and experimental study to elucidate the origin of the long thermal hal…

Molecular orbital studies on the mechanism of catalytic isomerization of xylenes II. The photochemical process

1981

Abstract The feasibility of an intermediate step in the mechanism of photochemical isomerization of xylenes in acidic media is explored by using CNDO molecular orbital methods. Along the reaction path from 2,6-dimethylbenzenium ion to dimethylbicyclo[3.1.0]hexenyl cation, the energy surfaces for this intermediate step have been drawn both for the first singlet S1 and triplet T1 excited states. The energies of these excited states have been calculated by adding to the ground-state energy calculated by CNDO/2 method the excitation energy calculated by CNDO/S-CI method. An optimization of the saddle point energy is achieved by introducing the angle between methyl groups and the ring plane as a…

Cadmium clusters in CdI2layered crystals: the influence on the optical properties

2007

The influence of overstoichiometric Cd i atoms on the optical properties of cadmium iodide layered crystals has been investigated. The results of optical absorption, luminescence, and luminescence excitation studies of CdI 2 crystals with controlled deviation from stoichiometric composition allow observing correlations between the Cd i concentration and features in absorption and emission spectra up to concentrations of 10 18 cm -3 . At higher concentrations the overstoichiometric cadmium atoms form clusters, which were observed using scanning electron microscopy. The extinction spectra of (CdI i ) n clusters are calculated in the frame of Mie theory and are found to correlate with the opti…

Enhanced network activity despite clinical recovery in experimental neuroinflammation using two-photon calcium imaging

2014

Determining cantilever stiffness from thermal noise

2013

We critically discuss the extraction of intrinsic cantilever properties, namely eigenfrequency fn, quality factor Qn and specifically the stiffness kn of the nth cantilever oscillation mode from thermal noise by an analysis of the power spectral density of displacement fluctuations of the cantilever in contact with a thermal bath. The practical applicability of this approach is demonstrated for several cantilevers with eigenfrequencies ranging from 50 kHz to 2 MHz. As such an analysis requires a sophisticated spectral analysis, we introduce a new method to determine kn from a spectral analysis of the demodulated oscillation signal of the excited cantilever that can be performed in the frequ…

Damming an electronic energy reservoir: ion-regulated electronic energy shuttling in a [2]rotaxane

2021

We demonstrate the first example of bidirectional reversible electronic energy transfer (REET) between the mechanically bonded components of a rotaxane. Our prototypical system was designed such that photoexcitation of a chromophore in the axle results in temporary storage of electronic energy in a quasi-isoenergetic “reservoir” chromophore in the macrocycle. Over time, the emissive state of the axle is repopulated from this reservoir, resulting in long-lived, delayed luminescence. Importantly, we show that cation binding in the cavity formed by the mechanical bond perturbs the axle chromophore energy levels, modulating the REET process, and ultimately providing a luminescence read-out of c…