Search results for "iTED"

Molecular structures and vibrations of m-methylaniline in the S0 and S1 states studied by laser induced fluorescence spectroscopy and ab initio calcu…

2000

Abstract The UV fluorescence excitation and dispersed fluorescence spectra of a jet-cooled m-methylaniline have been obtained for the S1←S0 transition, in which some of the bands have been observed for the first time. The main spectral bands have been assigned by comparison with those of other relevant substituted benzenes. It was found that the spectra exhibit an important feature which is the internal rotation of the methyl group in the electronic ground and excited states. Ab initio calculations at MP2/6-31G* and CIS/6-31G* show that the optimized structure of m-methylaniline in the ground state is not planar with the amino group having sp3 hybridation-like character due to the existence…

A Metal-Free, Nonconjugated Polymer for Solar Photocatalysis

2017

Heterogeneous catalysts that can absorb light over the solar range are ideal for green photocatalysis. Recently, attention has been directed towards the generation of novel solar-light photocatalysts, in particular, metal-free polymers. Herein, it is demonstrated that a metal-free, nonconjugated, anthraquinone-based copolymer (poly[1,4-diamine-9,10-dioxoanthracene-alt-(benzene-1,4-dioic acid)] (COP)) with a strong absorption in the visible region is effective as a sunlight heterogeneous photocatalyst. As a proof of concept, it has been used to mineralize 2,5-dichlorophenol (2,5-DCP) in water under air and sunlight irradiation. The photocatalytic efficiency of COP compares well with that of …

Diastereomeric Differentiation in the Quenching of Excited States by Hydrogen Donors

2003

Boosting Vis/NIR Charge-Transfer Absorptions of Iron(II) Complexes by N-Alkylation and N-Deprotonation in the Ligand Backbone.

2017

Reversing the 3MLCT / 3MC excited state order in iron(II) complexes is a challenging objective, yet would finally result in longsought luminescent transition metal complexes with an earthabundant central ion. One approach to achieve this goal is based on low-energy charge transfer absorptions in combination with a strong ligand field. Coordinating electron rich and electron poor tridentate oligopyridine ligands with large bite angles at iron(II) enables both low-energy MLCT absorption bands around 590 nm and a strong ligand field. Variations of the electron rich ligand by introducing longer alkyl substituents destabilizes the iron(II) complex towards ligand substitution reactions while hard…

The triplet excited state of the biocative compound thiabendazole. Characterization and suitability as reporter for cyclodextrin complexation

2012

Fluorescence spectroscopy, laser flash photolysis (LPF), and density functional theory calculations have been performed to characterize the photobehavior of thiabendazole (1). Direct LFP of 1 results in the generation of a transient absorbing at λmax = 570 nm identified as the triplet excited state (31∗). The intersystem crossing quantum yield is 0.91, and the triplet energy is 288 kJ mol−1. The singlet–triplet energy gap is 84 kJ mol−1. The behavior of thiabendazole within CDs results in a marked enhancement of the triplet lifetime, this change is attributed to the mobility restrictions of included 1 imposed by the cyclodextrin cavities.

Vibronic structure in triatomic molecules : The hydrocarbon flame bands of the formyl radical (HCO). A theoretical study

1998

A theoretical study of the vibrational structure of the math 2A′ ground and math 2A′ excited states of the formyl radical, HCO, and its deuterated form, DCO, has been performed. The potential energy surfaces have been computed by means of a multiconfigurational perturbative method, CASPT2. The computed geometries and the harmonic and anharmonic frequencies are successfully compared to the available experimental information. The vibrational intensities of the transition math 2A′↔math 2A′ have been computed both for absorption and emission. The results lead to accurate determinations of several structural parameters and some reassignments of the vibrational transitions of the so-called hydroc…

Single molecule spectroscopy of multichromophoric assemblies

2003

We have investigated multichromophoric assemblies composed of a variable number of chromophores by single molecule spectroscopy. Specific spectral signatures have allowed to distinguish at the single molecule level between molecular dimers representing strong and weak electronic dipole-dipole coupling. By using fluorescence excitation spectroscopy at low temperature, the sharp purely electronic zero-phonon lines of single chromophores within a single dendrimer containing four chromophores could be isolated in the frequency domain.

Double-quantum nutations in a two-level spin system

1986

The transient oscillatory behavior of the nonlinear response of a two-level electron-spin system is experimentally investigated in a sample of glassy silica with ${E}_{1}^{\mathcal{'}}$ centers (S=(1/2)) at microwave frequency at T=4.2 K. The transient regime, excited by an intense step-modulated radiation tuned to double-quantum (DQ) resonance, is monitored by revealing the second-harmonic (SH) wave radiated by the spins undergoing DQ transitions. Time- and frequency-domain results show that the emitted SH wave has two components: the former, which vanishes at the DQ resonance, exhibits an overdamped transient regime, the latter consists of damped oscillations at a frequency which depends …

Unprecedented blue intrinsic photoluminescence from hyperbranched and linear polyethylenimines: Polymer architectures and pH-effects

2007

The intrinsic photoluminescence properties of hyperbranched polyethylenimines (PEIs) and their linear counterpart (LPEIs) have been studied in absence of any classical fluorescent probes. The comparison of the inherent fluorescence emission between hyperbranched polyethylenimines and their linear analogues demonstrates that linear polyamines are capable of producing strong intrinsic photoluminescence species having long excited lifetimes without need of having a tridimensional-branched structure. The creation of inherently fluorescent polymeric centers from hyperbranched and linear polyethyleimines can be modulated by specific chemical modification and oxidation of amine groups as well as b…

Vibrational relaxation of matrix-isolated carboxylic acid dimers and monomers.

2009

Femtosecond mid-IR transient absorption spectroscopy was used to probe the vibrational dynamics of formic acid and acetic acid isolated in solid argon following excitation of the fundamental transition of the carbonyl stretching mode. Carboxylic acids form extremely stable H-bonded dimers, hindering the study of the monomeric species at equilibrium conditions. The low-temperature rare-gas matrix isolation technique allows for a unique control over aggregation enabling the study of the monomer vibrational dynamics, as well as the dynamics of two distinct dimer structures (cyclic and open chain). This study provides insight into the role of the methyl rotor and hydrogen bonding in the vibrati…