Excited State Relaxation Research Articles

Ultrafast dynamics and relaxation pathways in Eu(III) complexes with fluorinated β–diketonate ligands

A series of novel β-diketonate Eu3+ complexes with minor variations in the chemical structure of the diketone ligand were systematically studied. Six Eu3+ coordination compounds based on β-diketones, bearing linear perfluorinated substituents of various length (C1, C2, C3 and C6) and fixed pyrazole moiety were obtained. In addition, two water molecules, 1,10-phenanthroline or 4,7-diphenyl-1,10-phenanthroline as an ancillary ligand in compounds with fixed β-diketone ligand were used. Their photophysical properties were investigated by UV–Vis absorption and time-resolved femtosecond transient (fs-TA) absorption spectroscopy techniques. In this study, we investigate the impact of ancillary ligands and the fluorinated chain length of β-diketone ligands on the ultrafast relaxation processes that occur in the ligand environment. Relying on the ultrafast transient absorption measurements, it was demonstrated that the extension of fluorinated chains of β-diketone ligand leads to decrease of first excited singlet and triplet states relaxation rates. The compound with excessively long chain C6F13 exhibits the slowest relaxation of the triplet state T1.Besides, variation in the ancillary ligand alters the electronic energy transfer pathways in the whole complex. It was established, that introducing 4,7-diphenyl-1,10-phenanthroline (bath) instead of 1,10-phenanthroline (phen) dramatically changing the electronic energy transfer dynamics in the whole coordination compound. On the basis of the fs-TA measurements we conclude the bath ligand act as acceptor of electronic energy of diketone ligand in the excited state.

Acridin-9(10H)-one based thermally activated delayed fluorescence emitter for highly efficient green OLED

It is crucial for thermally activated delayed fluorescence (TADF) emitters to have both high photoluminescence quantum yield (PLQY) and high reverse intersystem crossing rate (kRISC). A novel TADF emitter, namely 3,6-bis(3,6-bis(diphenylamino)-9H-carbazol-9-yl)-10-phenylacridin-9(10H)-one (3,6-DPCz-AD), was designed by introducing N3,N3,N6,N6-tetraphenyl-9H-carbazole-3,6-diamine (DPCz) at 3,6-sites of the acceptor acridin-9(10H)-one (AD) by nucleophilic substitution. On the acridin-9(10H)-one ring, the sp2-hybridization of the 10-site N atom leads to high rigidity, which inhibited conformation relaxation of excited state to reduce non-radiative decay. The introduction of large conjugated diphenylamine groups at the 3,6-sites of carbazole not only facilitated the RISC by increasing intramolecular charge transfer and generating a low S1-T1 energy gap (ΔEST), but also enhanced the radiative transition by enlarging the highest occupied molecular orbital (HOMO) delocalization. As a result, even without the traditional highly distorted structure, 3,6-DPCz-AD exhibited strong TADF characteristics with high kRISC of 5.8 × 105 s−1, high kr of 3.4 × 107 s−1 and a high PLQY of 99% simultaneously. The green organic light-emitting diode (OLED) of 3,6-DPCz-AD showed both a maximum external quantum efficiency (EQEmax) of 30.1% and a power efficiency of 83.3 lm W−1. An EQE of 20.1% was still remained at a high brightness of 1000 cd m−2. This is one of the best performances for acridin-9(10H)-one based TADF emitters ever reported so far.

Processes triggered in guanine quadruplexes by direct absorption of UV radiation: From fundamental studies toward optoelectronic biosensors.

Guanine quadruplexes (GQs) are four-stranded DNA/RNA structures exhibiting an important polymorphism. During the past two decades, their study by time-resolved spectroscopy, from femtoseconds to milliseconds, associated to computational methods, shed light on the primary processes occurring when they absorb UV radiation. Quite recently, their utilization in label-free and dye-free biosensors was explored by a few groups. In view of such developments, this review discusses the outcomes of the fundamental studies that could contribute to the design of future optoelectronic biosensors using fluorescence or charge carriers stemming directly from GQs, without mediation of other molecules, as it is the currently the case. It explains how the excited state relaxation influences both the fluorescence intensity and the efficiency of low-energy photoionization, occurring via a complex mechanism. The corresponding quantum yields, determined with excitation at 266/267 nm, fall in the range of (3.0-9.5) × 10-4 and (3.2-9.2) × 10-3 , respectively. These values, significantly higher than the corresponding values found for duplexes, depend strongly on certain structural factors (molecularity, metal cations, peripheral bases, number of tetrads …) which intervene in the relaxation process. Accordingly, these features can be tuned to optimize the desired signal.

Overlooked Transformation of Nitrated Polycyclic Aromatic Hydrocarbons in Natural Waters: Role of Self-Photosensitization.

Photochemical transformation is an important process that involves trace organic contaminants (TrOCs) in sunlit surface waters. However, the environmental implications of their self-photosensitization pathway have been largely overlooked. Here, we selected 1-nitronaphthalene (1NN), a representative nitrated polycyclic aromatic hydrocarbon, to study the self-photosensitization process. We investigated the excited-state properties and relaxation kinetics of 1NN after sunlight absorption. The intrinsic decay rate constants of triplet (31NN*) and singlet (11NN*) excited states were estimated to be 1.5 × 106 and 2.5 × 108 s-1, respectively. Our results provided quantitative evidence for the environmental relevance of 31NN* in waters. Possible reactions of 31NN* with various water components were evaluated. With the reduction and oxidation potentials of -0.37 and 1.95 V, 31NN* can be either oxidized or reduced by dissolved organic matter isolates and surrogates. We also showed that hydroxyl (•OH) and sulfate (SO4•-) radicals can be generated via the 31NN*-induced oxidation of inorganic ions (OH- and SO42-, respectively). We further investigated the reaction kinetics of 31NN* and OH- forming •OH, an important photoinduced reactive intermediate, through complementary experimental and theoretical approaches. The rate constants for the reactions of 31NN* with OH- and 1NN with •OH were determined to be 4.22 × 107 and 3.95 ± 0.01 × 109 M-1 s-1, respectively. These findings yield new insights into self-photosensitization as a pathway for TrOC attenuation and provide more mechanistic details into their environmental fate.

Watching Excited State Dynamics with Optical and X-ray Probes: The Excited State Dynamics of Aquocobalamin and Hydroxocobalamin.

Femtosecond time-resolved X-ray absorption (XANES) at the Co K-edge, X-ray emission (XES) in the Co Kβ and valence-to-core regions, and broadband UV-vis transient absorption are combined to probe the femtosecond to picosecond sequential atomic and electronic dynamics following photoexcitation of two vitamin B12 compounds, hydroxocobalamin and aquocobalamin. Polarized XANES difference spectra allow identification of sequential structural evolution involving first the equatorial and then the axial ligands, with the latter showing rapid coherent bond elongation to the outer turning point of the excited state potential followed by recoil to a relaxed excited state structure. Time-resolved XES, especially in the valence-to-core region, along with polarized optical transient absorption suggests that the recoil results in the formation of a metal-centered excited state with a lifetime of 2-5 ps. This combination of methods provides a uniquely powerful tool to probe the electronic and structural dynamics of photoactive transition-metal complexes and will be applicable to a wide variety of systems.

Resolving the Emission Transition Dipole Moments of Single Doubly Excited Seeded Nanorods via Heralded Defocused Imaging.

Semiconductor nanocrystal emission polarization is a crucial probe of nanocrystal physics and an essential factor for nanocrystal-based technologies. While the transition dipole moment for the lowest excited state to ground state transition is well characterized, the dipole moment of higher multiexcitonic transitions is inaccessible via most spectroscopy techniques. Here, we realize direct characterization of the doubly excited-state relaxation transition dipole by heralded defocused imaging. Defocused imaging maps the dipole emission pattern onto a fast single-photon avalanche diode detector array, allowing the postselection of photon pairs emitted from the biexciton-exciton emission cascade and resolving the differences in transition dipole moments. Type-I1/2 seeded nanorods exhibit higher anisotropy of the biexciton-to-exciton transition compared to the exciton-to-ground state transition. In contrast, type-II seeded nanorods display a reduction of biexciton emission anisotropy. These findings are rationalized in terms of an interplay between the transient dynamics of the refractive index and the excitonic fine structure.

Sequential Multistep Excited-State Structural Transformations in N,N'-Diphenyl-dihydrodibenzo[a,c]phenazine Fluorophores.

We demonstrate that a single polycyclic π-scaffold can undergo sequential multistep excited-state structural evolution along the bent, planar, and twisted conformers, which coexist to produce intrinsic multiple fluorescence emissions in room-temperature solution. By installing a methyl or trifluoromethyl group on the ortho-site of N,N'-diphenyl-dihydrodibenzo[a,c]phenazine (DPAC), the enhanced steric effects change the fluorescence emission of DPAC from a dominant red band to well-resolved triple bands. The ultra-broadband triple emissions of ortho-substituted DPACs range from ≈350 to ≈850 nm, which is unprecedented for small fluorophores with molecular weight of <500. Ultrafast spectroscopy and theoretical calculations clearly reveal that the above dramatic changes originate from the influence of steric hindrance on the shape of excited state potential energy surface (S1 PES). Compared to the steep S1 PES of parental DPAC, the introduction of ortho-substituent is shown to make the path of structural evolution in S1 wider and flatter, so the ortho-substituted derivatives exhibit slower structural transformations from bent to planar and then to twisted forms, yielding intrinsic triple emission. The results provide the proof of concept that the bent, planar, and twisted emissive states can coexist in the same S1 PES, which greatly expand the fundamental understanding of the excited-state structural relaxation.

Ab Initio Simulation of the Ultrafast Circular Dichroism Spectrum of Provitamin D Ring-Opening.

We present a method to simulate ultrafast pump-probe time-resolved circular dichroism (TRCD) spectra based on time-dependent density functional theory trajectory surface hopping. The method is applied to simulate the TRCD spectrum along the photoinduced ring-opening of provitamin D. Simulations reveal that the initial decay of the signal is due to excited state relaxation, forming the rotationally flexible previtamin D. We further show that oscillations in the experimental TRCD spectrum arise from isomerizations between previtamin D rotamers with different chirality, which are associated with the helical conformation of the triene unit. We give a detailed description of the formation dynamics of different rotamers, playing a key role in the natural regulation of vitamin D photosynthesis. Going beyond the sole extraction of decay rates, simulations greatly increase the amount of information that can be retrieved from ultrafast TRCD, making it a sensitive tool to unravel details in the subpicosecond dynamics of photoinduced chirality changes.

Ultrafast Intermolecular Energy Transfer in OLED Materials: Excited-State Dynamics of a Blend of Poly(vinylcarbazole) and Oxadiazole Derivative in Solution and Film States

Intermolecular energy transfer dynamics between layers of organic materials controls the efficiency of organic light-emitting diode (OLED) devices. Here, to understand the ultrafast intermolecular energy transfer dynamics occurring in widely used UV-OLED materials of poly(vinylcarbazole) (PVK, donor: hole-transporting material) and synthesized oxadiazole derivative (OXD, acceptor: electron-transporting material), their excited-state relaxation pathways are investigated in tetrahydrofuran (THF) and film. Upon addition of OXD, the nanosecond fluorescence lifetime studies of PVK exhibited efficient quenching of dynamics, supporting the occurrence of Förster resonance energy transfer from PVK to OXD with an efficiency of ∼90%. The femtosecond time-resolved absorption measurements of the mixture of PVK and OXD revealed the intermolecular resonance energy transfer with a time constant of ∼1.32 ps from all of the intermediates in the excited states of PVK to OXD. Interestingly, in the film state, the formation of exciplex beneficial for devices with a lifetime of ∼32.66 ns was observed at ∼516 nm upon excitation of PVK in a blend of OXD and PVK. Nanosecond transient absorption spectra confirmed the occurrence of energy transfer also from the triplet state of PVK. Understanding of these excited-state dynamics occurring in solution and film states is a prerequisite to design and improve the performance of OLED materials.

Ultrafast excited-state energy dissipation pathway of diethylamino hydroxybenzoyl hexyl benzoate (DHHB) via the nanoparticles.

The organic UVA filter is popularized in sunscreen cosmetics due to the advantages of excellent light stability and high molar extinction coefficient. However, the poor water solubility of organic UV filters has been a common problem. Given that nanoparticles (NPs) can significantly improve the water solubility of organic chemicals. Meanwhile, the excited-state relaxation pathways of NPs might differ from their solution. Here, the NPs of diethylamino hydroxybenzoyl hexyl benzoate (DHHB), a popular organic UVA filter, were prepared by an advanced ultrasonic micro-flow reactor. The surfactant (sodium dodecyl sulfate) was selected as an effective stabilizer to prevent the self-aggregation of the NPs for DHHB. Femtosecond transient ultrafast spectroscopy (fs-TA) and theoretical calculations were utilized to trace and explain the excited-state evolution of DHHB in NPs suspension and its solution. The results reveal that the surfactant-stabilized NPs of DHHB reserve a similarly good performance of ultrafast excited-state relaxation. The stability characterization experiments demonstrate that the strategy of surfactant-stabilized NPs for sunscreen chemicals can maintain its stability and enhance the water solubility of DHHB compared with that of the solution phase. Therefore, the surfactant-stabilized NPs of organic UV filters are an effective method to improve water solubility and keep the stability from aggregation and photoexcitation.

Deep blue thermally activated delayed fluorescent emitters based on methyl-modified acridin-9(10H)-one acceptor

Developing deep blue thermally activated delayed fluorescence (TADF) materials with high efficiencies and good color purities is still a formidable challenge. Here, two novel deep blue TADF emitters, namely MePhCz-AD and MePhCz-AD-Py, were synthesized by incorporating two 3,6-diphenyl-9H-carbazole donors onto the methyl-modified acridin-9(10H)-one (AD) acceptor, respectively. The high rigidity of AD acceptor effectively suppressed non-radiative transition and vibration relaxation of excited states, which is favorable for a good emitting quantum yield and narrow spectral width. The presence of methyl groups at 2,7-sites of AD ring slightly reduced the acceptor strength and contributed to the deep blue emission color. Incorporation of phenyls at 3,6-sites of carbazole ring delocalized the distribution of the highest occupied molecular orbital (HOMO), promoting the radiative decay process. As a result, these two emitters showed deep blue TADF with fast radiative decay rates kR > 107 s−1. In addition, with the introduction of pyridyl (Py) group at 10-site of AD ring instead of phenyl, both the spin-orbital coupling (SOC) constant between high-lying triplet states and the lowest singlet excited state (S1) and thus the reverse intersystem crossing rate constant (kRISC) were dramatically promoted for MePhCz-AD-Py. The organic light-emitting diode with MePhCz-AD-Py as doped emitter exhibited a maximum external quantum efficiency (EQEmax) of 15.4% with a relatively narrow FWHM of 60 nm and the deep-blue color coordinates of (0.15, 0.15).

Rationalizing the environment-dependent photophysical behavior of a DNA luminescent probe by classical and non-adiabatic molecular dynamics simulations.

Environment-sensitive fluorescent nucleoside analogs are of utmost importance to investigate the structure of nucleic acids, their intrinsic flexibility, and sequence-specific DNA- and RNA-binding proteins. The latter play indeed a key role in transcription, translation as well as in the regulation of RNA stability, localization and turnover, and many other cellular processes. The sensitivity of the embedded fluorophore to polarity, hydration, and base stacking is clearly dependent on the specific excited-state relaxation mechanism and can be rationalized combining experimental and computational techniques. In this work, we elucidate the mechanisms leading to the population of the triplet state manifold for a versatile nucleobase surrogate, namely the 2-thienyl-3-hydroxychromone in gas phase, owing to non-adiabatic molecular dynamics simulations. Furthermore, we analyze its behavior in the B-DNA environment via classical molecular dynamics simulations, which evidence a rapid extrusion of the adenine facing the 2-thienyl-3-hydroxychromone nucleobase surrogate. Our simulations provide new insights into the dynamics of this family of chromophores, which could give rise to an integrated view and a fine tuning of their photochemistry, and namely the role of excited-state intramolecular proton transfer for the rational design of the next generation of fluorescent nucleoside analogs.

Ferricyanide photo-aquation pathway revealed by combined femtosecond Kβ main line and valence-to-core x-ray emission spectroscopy

Reliably identifying short-lived chemical reaction intermediates is crucial to elucidate reaction mechanisms but becomes particularly challenging when multiple transient species occur simultaneously. Here, we report a femtosecond x-ray emission spectroscopy and scattering study of the aqueous ferricyanide photochemistry, utilizing the combined Fe Kβ main and valence-to-core emission lines. Following UV-excitation, we observe a ligand-to-metal charge transfer excited state that decays within 0.5 ps. On this timescale, we also detect a hitherto unobserved short-lived species that we assign to a ferric penta-coordinate intermediate of the photo-aquation reaction. We provide evidence that bond photolysis occurs from reactive metal-centered excited states that are populated through relaxation of the charge transfer excited state. Beyond illuminating the elusive ferricyanide photochemistry, these results show how current limitations of Kβ main line analysis in assigning ultrafast reaction intermediates can be circumvented by simultaneously using the valence-to-core spectral range.

Study on Plasma Combustion in Aeroengine Combustor

To explore the plasma combustion affect the performance of the aircraft engine combustor, 16 components in the aviation kerosene 25-step reaction mechanism on the basis of considering step 9 simplify the plasma reaction mechanism, set up considering plasma electron collision reaction excited state relaxation and excited states participate in the process of chemical reaction kerosene combustion reaction model, The numerical calculation of the combustion process in the combustor is carried out, and the numerical calculation results of the combustion process with or without plasma combustion are compared and analyzed. The results show that the core reaction zone of the combustion chamber fuel is relatively forward under the conventional mechanism condition, and the average temperature of the combustion chamber outlet is 1910K. The temperature and high-temperature zone of the combustor where the plasma mechanism is applied are mainly distributed in the combustor outlet, mixing hole and main combustion hole, and the average temperature is 2050K. Meanwhile, the kerosene combustion efficiency also increases from 82.4% to 90.1%, increasing by about 7.7%. The results show that the addition of a plasma mechanism can deepen the chemical reaction degree of kerosene and release more heat to improve the combustion efficiency of kerosene.

Dynamics of the Ligand Excited States Relaxation in Novel β-Diketonates of Non-Luminescent Trivalent Metal Ions.

Complexes emitting in the blue spectral region are attractive materials for developing white-colored light sources. Here, we report the luminescence properties of novel coordination compounds based on the trivalent group 3, 13 metals, and the 1-phenyl-3-methyl-4-cyclohexylcarbonyl-pyrazol-5-onate (QCH) ligand. [M(QCH)3] (M = Al, Ga, and In), [M(QCH)3(H2O)] (M = Sc, Gd, and Lu), [Lu(QCH)3(DMSO)], and [La(QCH)3(H2O)(EtOH)] complexes were synthesized and structurally characterized by a single-crystal X-ray diffraction study. It has been found that the luminescence quantum yields of the ligand increase by one order of magnitude upon metal coordination. A significant correspondence between the energies of the ligand's excited states and the luminescence quantum yields to the metal ion's atomic numbers was found using molecular spectroscopy techniques. The replacement of the central ion with the heavier one leads to a monotonic increase in singlet state energy, while the energy of the triplet state is similar for all the complexes. Time-resolved measurements allowed us to estimate the intersystem crossing (ISC) rate constants. It was shown that replacing the Al3+ ion with the heavier diamagnetic Ga3+ and In3+ ions decreased the ISC rate, while the replacement with the paramagnetic Gd3+ ion increased the ISC rate, which resulted in a remarkably bright and room-temperature phosphorescence of [Gd(QCH)3(H2O)].

Conformational effect on the photophysics of two BODIPY dyes in a mixture of butanol and acetonitrile: Insight from the steady-state, fluorescence time-resolved spectroscopy and TD-DFT calculations

We studied the effect of acetonitrile-butanol-1 mixture composition on the photophysics (absorption, fluorescence emission spectra, the quantum yield as well as the relaxation of the excited state) of two BODIPY derivatives with an aryl and pyridine substituent in the meso position and methyl (ethyl) in α,β-position. The behavior of these photophysical properties (fluorescence quantum yields, fluorescence lifetimes, radiative and nonradiative constants) as a function of the mixture composition points to its correlation with the rotation of the phenyl group that is possible in BDP2 while it is hindered in BDP1 as a channel of the excited state energy relaxation. As a consequence, the photophysical properties of BDP1 are weakly dependent on the mixture composition while those of BPD2 undergo two stages of variation. In the low mole fraction of Butanol-1 (lower than 0.48), where the viscosity changes by 0.8 MPa.s, the BDP2 photophysical properties are slightly dependent on the mixture composition. We conjecture that the free rotation of the phenyl group allows both radiative and nonradiative excited state relaxation to occur. This is shown by a relatively high fluorescence quantum yield and nonradiative constant values that remain constant in this range of butanol-1 mol fraction. For its further increase, the photophysical properties become strongly dependent on the change of the mixture composition and this was associated with the gradual increase of the viscosity by a factor of 1.7 MPa.s that results in a hindrance of the rotation of the phenyl group. This makes 8-phenyl substituted BDP2 a sensitive molecular rotor for small changes in viscosity between 0.2 and 3 MPa.s.

Local electronic structure of interstitial hydrogen in MgH2 inferred from muon study

Magnesium hydride has great potential as a solid hydrogen (H) storage material because of its high H storage capacity of 7.6 wt%. However, its slow hydrogenation and dehydrogenation kinetics and the high temperature of 300 ∘C required for decomposition are major obstacles to small-scale applications such as automobiles. The local electronic structure of interstitial H in MgH2 is an important fundamental knowledge in solving this problem, which has been studied mainly based on density functional theory (DFT). However, few experimental studies have been performed to assess the results of DFT calculations. We have therefore introduced muon (Mu) as pseudo-H into MgH2 and investigated the corresponding interstitial H states by analyzing their electronic and dynamical properties in detail. As a result, we observed multiple Mu states similar to those observed in wide-gap oxides, and found that their electronic states can be attributed to relaxed–excited states associated with donor/acceptor levels predicted by the recently proposed ‘ambipolarity model’. This provides an indirect support for the DFT calculations on which the model is based via the donor/acceptor levels. An important implication of the muon results for improved hydrogen kinetics is that dehydrogenation, serving as a reduction for hydrides, stabilises the interstitial H− state.

Diazadiboraacenes: Synthesis, Spectroscopy and Computations.

The incorporation of heteroatoms into hydrocarbon compounds greatly expands the chemical space of molecular materials. In this context, B-N doping takes a center stage due to its isosterism with a C=C-bond. Herein, we present a new and modular synthetic concept to access novel diazadiborabenzo[b]triphenylenes 7 a-h using the B-N doped biradical 16 as intermediate. Characterization of the photophysical properties revealed the emission spectra of the diazadibora benzo[b]triphenylenes 7 a-h can conveniently be tuned by small changes of the substitution on the boron-atom. All of the diazadibora compounds show a short life-time phosphorescence. Additionally, we were able to rationalize the excited-state relaxation of the diazadiboraacene 7 a via intersystem crossing by quantum chemical calculations. The new synthetic strategy provides an elegant route to various novel B-N doped acenes with great potential for applications in molecular materials.

Understanding of Intramolecular Charge Transfer Dynamics of a Push–Pull Dimethylamino-phenylethynylphenyl-dicyanoimidazole by Steady-State and Ultrafast Spectroscopic Studies

Photophysical behaviors of D−π–A compound 2-{4-[4-(N,N-dimethylamino)phenylethynyl]phenyl-1-methyl-1H-imidazole-4,5-dicarbonitrile (DMAPPIDCN) were explored using steady-state absorption, fluorescence emission, and femtosecond time-resolved absorption and emission spectroscopic techniques at room temperature along with computational time-dependent density functional theory (TD-DFT) calculation. The spectroscopic studies were carried out in different solvents of varying polarities including binary solvent mixtures. The role of the solvent polarity, viscosity, and temperature on the relaxation mechanism of DMAPPIDCN is disclosed. The observed steady-state and time-resolved spectroscopic features were attributed to intramolecular charge transfer (ICT) dynamics. The ICT in DMAPPIDCN is rationalized to a sequential twisted motion of both N(CH3)2 and whole N,N-dimethylaminophenyl moieties around the molecular axis interconnecting the adjacent imidazolephenyl moiety leading to the TICT1 and TICT2 (σ*) states. The increased solvent polarity affected mostly the fluorescence emission spectra pointing to a significant increase in the excited state dipole moment. This result clearly reveals formation of the TICT2 (σ*) involving efficient charge transfer from the (N,N-dimethylamino)phenyl (DMAP) donor to the phenyl-1-methyl-1H-imidazole-dicarbonitrile (PIDCN) acceptor in the excited state in a polar environment. In the TICT2 (σ*) state, the planes of electron-withdrawing and electron-donating moieties are perpendicular with the angle (DMAP)C–C≡C being 141.1°. This nonplanar arrangement accounts for the observed large Stokes shift. Time-resolved fluorescence spectroscopic studies unveil the excited state relaxation processes confirming the increase in the nonradiative decay rate in aprotic medium with increase in the solvent dielectric constants. Femtosecond transient spectroscopic studies unambiguously confirmed the existence of well separated LE and TICT states and their ensuing kinetics in polar medium. In nonpolar solvents, DMAPPIDCN shows strong fluorescence which emits from the LE (ππ*) state, whereas in polar solvents, formation of two consecutive TICT states occurs from the LE (ππ*) in a sub picosecond to few picosecond time domain depending on polarity of the solvents and the non-radiative decay from the TICT states.

Femtosecond Time-Resolved Observation of Relaxation and Wave Packet Dynamics of the S1 State in Electronically Excited o-Fluoroaniline

Quantum beat frequency is the basis for understanding interference effects and vibrational wave packet dynamics and has important applications. Using femtosecond time-resolved mass spectrometry and femtosecond time-resolved photoelectron image combined with theoretical calculations, we study the electronic excited-state relaxation of o-fluoraniline molecule and the time-dependent evolution of vibrational wave packets between different eigenstates. After the molecule absorbs a photon of 288.3 nm and is excited to the S1 state, intramolecular vibrational redistribution first occurs on the time scale τ1 = 349 fs, and then the transition to the triplet state occurs through the intersystem crossing on the time scale τ2 = 583 ps, and finally, the triplet state occurs decays slowly through the time scale τ3 = 2074 ps. We find the intramolecular vibrational redistribution is caused by the 00, 10b1 and 16a1 vibrational modes of the Sl state origin. That is, the 288.3 nm femtosecond laser excites the molecule to the S1 state, and the continuous flow of the vibrational wave packet prepares a coherent superposition state of three vibrational modes. Through extracting the oscillation of different peak intensities in the photoelectron spectrum, we observe reversible changes caused by mutual interference of the S1 00, S1 10b1 and S1 16a1 states when the wave packets flow. When the pump pulse is 280 nm, the beat frequency disappears completely. This is explained in terms of increases in the vibrational field density and characteristic period of oscillation, and statistical averaging makes the quantum effect smooth and indistinguishable. In addition, the Rydberg component of the S1 state is more clearly resolved by combining experiment and theory.