Search results for "Singlet"
showing 10 items of 352 documents
On the intrinsic population of the lowest triplet state of uracil
2007
Abstract From CASPT2//CASSCF quantum-chemical computations it is determined that the lowest triplet state of uracil can be efficiently populated from the initially activated singlet manifold through respective singlet–triplet crossings of the singlet state with the low-lying 3nπ∗ state at 4.6 eV and with the lowest 3ππ∗ state at 4.2 eV located along the minimum energy path of the low-lying 1ππ∗ state. Large spin–orbit coupling elements predict, in particular for the former case, efficient intersystem crossing processes. The wavelength dependence measured for the triplet quantum yield can be explained by the location of the singlet–triplet crossing regions.
Quinoidal oligothiophenes: towards biradical ground-state species.
2009
A family of quinoidal oligothiophenes, from the dimer to the hexamer, with fused bis(butoxymethyl)cyclopentane groups has been extensively investigated by means of electronic and vibrational spectroscopy, electrochemical measurements, and density functional calculations. The latter predict that the electronic ground state always corresponds to a singlet state and that, for the longest oligomers, this state has biradical character that increases with increasing oligomer length. The shortest oligomers display closed-shell quinoidal structures. Calculations also predict the existence of very low energy excited triplet states that can be populated at room temperature. Aromatization of the conju…
A theoretical study of the intramolecular charge transfer in 4-(dimethylamino)benzethyne
2014
We have investigated the non-adiabatic relaxation processes occurring in the singlet manifold of 4-(dimethylamino)benzethyne (DMABE){,} a molecule isoelectronic with 4-(dimethylamino)benzonitrile (DMABN) but lacking its characteristic dual fluorescence{,} using multireference perturbation theory methods. The results obtained point out to the existence of a two-fold decay mechanism in which the population of the initially accessed La state bifurcates towards a locally excited (LE) and a [small pi][sigma]* state. Further relaxation to an emitting intramolecular charge transfer (ICT) state is impeded due to the presence of pronounced energy barriers along their associated potential energy surf…
Photodynamics of a Molecular Water-Soluble Nanocluster Identified as Au130(pMBA)50
2015
Photodynamics of a highly monodisperse sample of a water-soluble gold nanocluster tentatively identified as Au130(pMBA)50 (pMBA = p-mercaptobenzoic acid) was studied by mid-IR transient absorption spectroscopy with visible excitation. The observed long-lived excited states (>1 ns) indicate a molecular behavior of the cluster. By combining the transient absorption data with DFT calculation results the observed relaxation dynamics could be fully explained by identifying several relaxation processes involving singlet and triplet manifolds. The results indicate that the cluster may have interesting transient magnetic properties due to a long-lived triplet population.
Complete One-Loop Renormalization of the Higgs-Electroweak Chiral Lagrangian
2018
The electroweak sector of the Standard Model can be formulated in a way similar to Chiral Perturbation Theory (ChPT), but extended by a singlet scalar. The resulting effective field theory (EFT) is called Higgs-Electroweak Chiral Lagrangian (EWCh$\mathcal{L}$) and is the most general approach to new physics in the Higgs sector. It solely assumes the pattern of symmetry breaking leading to the three electroweak Goldstone bosons (i.e. massive $W$ and $Z$) and the existence of a Higgs-like scalar particle. The power counting of the EWCh$\mathcal{L}$ is given by a generalization of the momentum expansion of ChPT. It is connected to a loop expansion, making the theory renormalizable order by ord…
Through space singlet-singlet and triplet-triplet energy transfers in cofacial bisporphyrins held by the carbazoyl spacer
2007
The through space singlet-singlet and triplet-triplet energy transfers in cofacial bis(etio-porphyrins) rigidly held by the carbazoyl spacer were investigated. The studies on singlet-singlet transfer, which operates via a Förster mechanism, were performed using the zinc porphyrin and free base chromophores as energy donor and acceptor, respectively, while the investigation on triplet-triplet processes was performed using the palladium porphyrin, and the zinc porphyrin and free base chromophores as donor and acceptors, respectively. The rate for singlet-singlet transfer ( k ET ( singlet )) is unexpectedly slower than that reported for other similar, rigidly held bisporphyrins such as H 2( D…
QCD resummation effects in forward $J/\psi$ and very backward jet inclusive production at the LHC
2017
We propose and study the inclusive production of a forward $J/\psi$ and a very backward jet at the LHC as an observable to reveal high-energy resummation effects \`a la BFKL. Our different predictions are based on the various existing mechanisms to describe the production of the $J/\psi$, namely, NRQCD singlet and octet contributions, and the color evaporation model.
Induced Night-Vision by Singlet-Oxygen-Mediated Activation of Rhodopsin
2019
In humans, vision is limited to a small fraction of the whole electromagnetic spectrum. One possible strategy for enhancing vision in deep-red or poor-light conditions consists of recruiting chlorophyll derivatives in the rod photoreceptor cells of the eye, as suggested in the case of some deep-sea fish. Here, we employ all-atom molecular simulations and high-level quantum chemistry calculations to rationalize how chlorin e6 (Ce6), widely used in photodynamic therapy although accompanied by enhanced visual sensitivity, mediates vision in the dark, shining light on a fascinating but largely unknown molecular mechanism. First, we identify persistent interaction sites between Ce6 and the extra…
<i>Geminal</i> Parahydrogen-Induced Polarization: Accumulating Long-Lived Singlet Order on Methylene Proton Pairs
2020
Abstract. In the majority of hydrogenative PHIP (Parahydrogen Induced Polarization) experiments, the hydrogen molecule undergoes pairwise cis-addition to an unsaturated precursor to occupy vicinal positions on the product molecule. However, some ruthenium-based hydrogenation catalysts induce geminal hydrogenation, leading to a reaction product in which the twohydrogen atoms are transferred to the same carbon center, forming a methylene (CH2) group. The singlet order of parahydrogen is substantially retained over the geminal hydrogenation reaction, giving rise to a singlet-hyperpolarized CH2 group. Although the T1 relaxation times of the methylene protons are often short, the singlet order h…
Effect of gases on biochemical stabilization
2019
International audience; Lipid or protein are sensitive to peroxidation and inert gas limit or stop adulterations. Unsaturated lipids are peroxided by ground state dioxygen in presence of catalysts (iron, enzymes) or after thermal dissociation of C=C bond, and by excited state dioxygen without any assistance (photo-oxidation). Inerting fragile oils by bubbling with dinitrogen or carbon dioxide that are soluble gas in oil slows oxidation process during storage or frying. In a same way, limit the oxidation of the tryptophan residues of protein is possible by reducing oxygen content. Oxidation leads also to oxidation of thiol in disulfide, which induced protein cross-linked and decay of functio…