Browse
Submit Data
Databases
API
Help

Dataset Information

28 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

The excited-state dynamics of the radical anions of cyanoanthracenes.

ABSTRACT: The radical anion of 9,10-dicyanoanthracene (DCA) has been suggested to be a promising chromophore for photoredox chemistry, due to its nanosecond excited-state lifetime determined from indirect measurements. Here, we investigate the excited-state dynamics of the radical anion of three cyanoanthracenes, including DCA˙-, produced by photoinduced electron transfer in liquid using both pump-probe and pump-pump probe transient electronic absorption spectroscopy. All three excited radical ions are characterised by a 3-5 ps lifetime, due to efficient non-radiative deactivation to the ground state. The decay pathway most probably involves D₁/D₀ conical intersection(s), whose presence is favoured by the enhanced flexibility of the radical anions relative to their neutral counterparts. The origin of the discrepancy with the nanosecond lifetime of DCA˙-* reported previously is discussed. These very short lifetimes limit, but do not preclude, photochemical applications of the cyanoanthracene anions.

SUBMITTER: Beckwith JS

PROVIDER: S-EPMC8694058 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Excited state dynamics for visible-light sensitization of a photochromic benzil-subsituted phenoxyl-imidazolyl radical.

Project description:Visible-light sensitized photoswitches have been paid particular attention in the fields of life sciences and materials science because long-wavelength light reduces photodegradation, transmits deep inside of matters, and achieves the selective excitation in condensed systems. Among various photoswitch molecules, the phenoxyl-imidazolyl radical complex (PIC) is a recently developed thermally reversible photochromic molecule whose thermal back reaction can be tuned from tens of nanoseconds to tens of seconds by rational design of the molecular structure. While the wide range of tunability of the switching speed of PIC opened up various potential applications, no photosensitivity to visible light limits its applications. In this study, we synthesized a visible-light sensitized PIC derivative conjugated with a benzil unit. Femtosecond transient absorption spectroscopy revealed that the benzil unit acts as a singlet photosensitizer for PIC by the Dexter-type energy transfer. Visible-light sensitized photochromic reactions of PIC are important for expanding the versatility of potential applications to life sciences and materials science.

| S-EPMC6808191 | biostudies-literature

Nonadiabatic Excited-State Dynamics with Machine Learning.

Project description:We show that machine learning (ML) can be used to accurately reproduce nonadiabatic excited-state dynamics with decoherence-corrected fewest switches surface hopping in a 1-D model system. We propose to use ML to significantly reduce the simulation time of realistic, high-dimensional systems with good reproduction of observables obtained from reference simulations. Our approach is based on creating approximate ML potentials for each adiabatic state using a small number of training points. We investigate the feasibility of this approach by using adiabatic spin-boson Hamiltonian models of various dimensions as reference methods.

| S-EPMC6174422 | biostudies-literature

Excited State Dynamics of Thermally Activated Delayed Fluorescence from an Excited State Intramolecular Proton Transfer System.

Project description:We describe the photophysical processes that give rise to thermally activated delayed fluorescence in the excited state intramolecular proton transfer (ESIPT) molecule, triquinolonobenzene (TQB). Using transient absorption and time-resolved photoluminescence spectroscopy, we fully characterize prompt and delayed emission, phosphorescence, and oxygen quenching to reveal the reverse intersystem crossing mechanism (rISC). After photoexcitation and rapid ESIPT to the TQB-TB tautomer, emission from S1 is found to compete with thermally activated ISC to an upper triplet state, T2, very close in energy to S1 and limiting photoluminescence quantum yield. T2 slowly decays to the lowest triplet state, T1, via internal conversion. In the presence of oxygen, T2 is quenched to the ground state of the double proton transferred TQB-TC tautomer. Our measurements demonstrate that rISC in TQB occurs from T2 to S1 driven by thermally activated reverse internal conversion from T1 to T2 and support recent calculations by Cao et al. (Cao, Y.; Eng, J.; Penfold, T. J. Excited State Intramolecular Proton Transfer Dynamics for Triplet Harvesting in Organic Molecules. J. Phys. Chem. A 2019, 123, 2640-2649).

| S-EPMC7304890 | biostudies-literature

Chromophore-radical excited state antiferromagnetic exchange controls the sign of photoinduced ground state spin polarization.

Project description:A change in the sign of the ground-state electron spin polarization (ESP) is reported in complexes where an organic radical (nitronylnitroxide, NN) is covalently attached to a donor-acceptor chromophore via two different meta-phenylene bridges in (bpy)Pt(CAT-m-Ph-NN) (mPh-Pt) and (bpy)Pt(CAT-6-Me-m-Ph-NN) (6-Me-mPh-Pt) (bpy = 5,5'-di-tert-butyl-2,2'-bipyridine, CAT = 3-tert-butylcatecholate, m-Ph = meta-phenylene). These molecules represent a new class of chromophores that can be photoexcited with visible light to produce an initial exchange-coupled, 3-spin (bpy˙-, CAT+˙ = semiquinone (SQ), and NN), charge-separated doublet 2S1 (S = chromophore excited spin singlet configuration) excited state. Following excitation, the 2S1 state rapidly decays to the ground state by magnetic exchange-mediated enhanced internal conversion via the 2T1 (T = chromophore excited spin triplet configuration) state. This process generates emissive ground state ESP in 6-Me-mPh-Pt while for mPh-Pt the ESP is absorptive. It is proposed that the emissive polarization in 6-Me-mPh-Pt results from zero-field splitting induced transitions between the chromophoric 2T1 and 4T1 states, whereas predominant spin-orbit induced transitions between 2T1 and low-energy NN-based states give rise to the absorptive polarization observed for mPh-Pt. The difference in the sign of the ESP for these molecules is consistent with a smaller excited state 2T1 - 4T1 gap for 6-Me-mPh-Pt that derives from steric interactions with the 6-methyl group. These steric interactions reduce the excited state pairwise SQ-NN exchange coupling compared to that in mPh-Pt.

| S-EPMC8549796 | biostudies-literature

PyUNIxMD: A Python-based excited state molecular dynamics package.

Project description:Theoretical/computational description of excited state molecular dynamics is nowadays a crucial tool for understanding light-matter interactions in many materials. Here we present an open-source Python-based nonadiabatic molecular dynamics program package, namely PyUNIxMD, to deal with mixed quantum-classical dynamics for correlated electron-nuclear propagation. The PyUNIxMD provides many interfaces for quantum chemical calculation methods with commercial and noncommercial ab initio and semiempirical quantum chemistry programs. In addition, the PyUNIxMD offers many nonadiabatic molecular dynamics algorithms such as fewest-switch surface hopping and its derivatives as well as decoherence-induced surface hopping based on the exact factorization (DISH-XF) and coupled-trajectory mixed quantum-classical dynamics (CTMQC) for general purposes. Detailed structures and flows of PyUNIxMD are explained for the further implementations by developers. We perform a nonadiabatic molecular dynamics simulation for a molecular motor system as a simple demonstration.

| S-EPMC8362049 | biostudies-literature

Excited-state vibration-polariton transitions and dynamics in nitroprusside.

Project description:Strong cavity coupling to molecular vibrations creates vibration-polaritons capable of modifying chemical reaction kinetics, product branching ratios, and charge transfer equilibria. However, the mechanisms impacting these molecular processes remain elusive. Furthermore, even basic elements determining the spectral properties of polaritons, such as selection rules, transition moments, and lifetimes are poorly understood. Here, we use two-dimensional infrared and filtered pump-probe spectroscopy to report clear spectroscopic signatures and relaxation dynamics of excited vibration-polaritons formed from the cavity-coupled NO band of nitroprusside. We apply an extended multi-level quantum Rabi model that predicts transition frequencies and strengths that agree well with our experiment. Notably, the polariton features decay ~3-4 times slower than the polariton dephasing time, indicating that they support incoherent population, a consequence of their partial matter character.

| S-EPMC7801531 | biostudies-literature

Can anions possess bound doubly-excited electronic states?

Project description:Anions play an important role in many fields of chemistry. Many molecules possess stable anions, but these anions often do not have stable electronic excited states and the anion loses its excess electron once excited. All the known stable valence excited states of anions are singly-excited states, i.e., valence doubly-excited states have not been reported. As excited states are relevant for numerous applications, and constitute basic properties, we searched for valence doubly-excited states which are stable, i.e., exhibit energies below that of the ground state of the respective neutral molecule. We concentrated on two promising prototype candidates, the anions of the smallest endocircular carbon ring Li@C12 and of the smallest endohedral fullerene Li@C20. By employing accurate state-of-the-art many-electron quantum chemistry methods, we investigated the low-lying excited states of these anions and found that they possess several low-lying stable singly-excited states and, in particular, a stable doubly-excited state each. It is noteworthy that the found doubly-excited state of Li@C12- possesses a cumulenic carbon ring in sharp contrast to the ground and singly-excited states. The findings shed light on how to design anions with stable valence singly- and doubly-excited states. Possible applications are mentioned.

| S-EPMC10321500 | biostudies-literature

Fabrication-Method-Dependent Excited State Dynamics in CH3NH3PbI3 Perovskite Films.

Project description:Understanding the excited-state dynamics in perovskite photovoltaics is necessary for progress in these materials, but changes in dynamics depending on the fabrication processes used for perovskite photoactive layers remain poorly characterised. Here we report a comparative study on femtosecond transient absorption (TA) in CH3NH3PbI3 perovskite films fabricated by various solution-processing methods. The grain sizes and the number of voids between grains on each film varied according to the film synthesis method. At the low excitation fluence of 0.37 ?J cm-2, fast signal drops in TA dyanmics within 1.5?ps were observed in all perovskite films, but the signal drop magnitudes differed becuase of the variations in charge migration to trap states and band gap renormalisation. For high excitation fluences, the buil-up time of the TA signal was increased by the activated hot-phonon bottleneck, while the signal decay rate was accelerated by fluence-dependent high-order charge recombination. These fluence-dependent dynamics changed for different perovskite fabrication methords, indicating that the dynamics were affected by morphological features such as grain sizes and defects.

| S-EPMC5705678 | biostudies-literature

Automatic Clustering of Excited-State Trajectories: Application to Photoexcited Dynamics.

Project description:We introduce automatic clustering as a computationally efficient tool for classifying and interpreting trajectories from simulations of photo-excited dynamics. Trajectories are treated as time-series data, with the features for clustering selected by variance mapping of normalized data. The L2-norm and dynamic time warping are proposed as suitable similarity measures for calculating the distance matrices, and these are clustered using the unsupervised density-based DBSCAN algorithm. The silhouette coefficient and the number of trajectories classified as noise are used as quality measures for the clustering. The ability of clustering to provide rapid overview of large and complex trajectory data sets, and its utility for extracting chemical and physical insight, is demonstrated on trajectories corresponding to the photochemical ring-opening reaction of 1,3-cyclohexadiene, noting that the clustering can be used to generate reduced dimensionality representations in an unbiased manner.

| S-EPMC10536988 | biostudies-literature

Excited-State Dynamics of Proflavine after Intercalation into DNA Duplex.

Project description:Proflavine is an acridine derivative which was discovered as one of the earliest antibacterial agents, and it has been proven to have potential application to fields such as chemotherapy, photobiology and solar-energy conversion. In particular, it is well known that proflavine can bind to DNA with different modes, and this may open addition photochemical-reaction channels in DNA. Herein, the excited-state dynamics of proflavine after intercalation into DNA duplex is studied using femtosecond time-resolved spectroscopy, and compared with that in solution. It is demonstrated that both fluorescence and the triplet excited-state generation of proflavine were quenched after intercalation into DNA, due to ultrafast non-radiative channels. A static-quenching mechanism was identified for the proflavine-DNA complex, in line with the spectroscopy data, and the excited-state deactivation mechanism was proposed.

| S-EPMC9738913 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data