The dependence of singlet exciton relaxation on excitation density and temperature in polycrystalline tetracene thin films: kinetic evidence for a dark intermediate state and implications for singlet fission

The excited state dynamics of polycrystalline tetracene films are studied using femtosecond transient absorption in combination with picosecond fluorescence, continuing work reported in an earlier paper [J. J. Burdett, A. M. Muller, D. Gosztola, and C. J. Bardeen, J. Chem. Phys. 133, 144506 (2010)]. A study of the intensity dependence of the singlet state decay is conducted to understand the origins of the discrepancy between the broadband transient absorption and fluorescence experiments seen previously. High-sensitivity single channel transient absorption experiments allow us to compare the transient absorption dynamics to the fluorescence dynamics measured at identical laser fluences. At high excitation densities, an exciton-exciton annihilation rate constant of ~1 × 10(-8) cm(3) s(-1) leads to rapid singlet decays, but at excitation densities of 2 × 10(17) cm(-3) or less the kinetics of the transient absorption match those of the fluorescence. At these lower excitation densities, both measurements confirm that the initially excited singlet state relaxes with a decay time of 80 ± 3 ps, not 9.2 ps as claimed in the earlier paper. In order to investigate the origin of the singlet decay, the wavelength-resolved fluorescence dynamics were measured at 298 K, 77 K, and 4 K. A high-energy J-type emitting species undergo a rapid (~100 ps) decay at all temperatures, while at 77 K and 4 K additional species with H-type and J-type emission lineshapes have much longer lifetimes. A global analysis of the wavelength-dependent decays shows that the initial ~100 ps decay occurs to a dark state and not via energy transfer to lower energy bright states. Varying the excitation wavelength from 400 nm to 510 nm had no effect on the fast decay, suggesting that there is no energy threshold for the initial singlet relaxation. The presence of different emitting species at different temperatures means that earlier interpretations of the fluorescence behavior in terms of one singlet state that is short-lived due to singlet fission at high temperatures but long-lived at lower temperatures are probably too simplistic. The presence of a rapid singlet decay at all temperatures indicates that the initially created J-type singlet exciton decays to an intermediate that only produces free triplets (and delayed fluorescence) at high temperatures.     

Low-temperature dynamics of weakly localized Frenkel excitons in disordered linear chains

We calculate the temperature dependence of the fluorescence Stokes shift and the fluorescence decay time in linear Frenkel exciton systems resulting from the thermal redistribution of exciton population over the band states. The following factors, relevant to common experimental conditions, are accounted for in our kinetic model: (weak) localization of the exciton states by static disorder, coupling of the localized excitons to vibrations in the host medium, a possible nonequilibrium of the subsystem of localized Frenkel excitons on the time scale of the emission process, and different excitation conditions (resonant or nonresonant). A Pauli master equation, with microscopically calculated transition rates, is used to describe the redistribution of the exciton population over the manifold of localized exciton states. We find a counterintuitive nonmonotonic temperature dependence of the Stokes shift. In addition, we show that depending on experimental conditions, the observed fluorescence decay time may be determined by vibration-induced intraband relaxation, rather than radiative relaxation to the ground state. The model considered has relevance to a wide variety of materials, such as linear molecular aggregates, conjugated polymers, and polysilanes.     

Molecular modeling and simulation of conjugated polymer oligomers: ground and excited state chain dynamics of PPV in the gas phase

The ground and excited state dynamics of poly(p-phenylenevinylene) (PPV) chains is studied through an implementation of mixed quantum/classical molecular dynamics simulation. The model used in the simulations combines the semiempirical Pariser-Parr-Pople (PPP) Hamiltonian to treat the pi molecular electronic structure with a mechanical force field capturing all other aspects. Nuclear degrees of freedom are treated classically. We first validate the model by simulating PPV chains of various length, and evaluate the absorption spectra. The thermal disorder contribution to the breadth of the first absorption band is estimated to be 0.2 eV at T = 300 K. To investigate the relationship between the emission and chain conformation, we simulate an isolated ten unit chain of PPV in the ground and the lowest excited state. The emission spectrum, red-shifted with respect to absorption of about 0.2 eV as found in experiments, shows a structured line shape that we relate to the photoinduced CC bond distortions. In accord with earlier studies, the exciton self-traps in the middle of the chain. We introduce two collective variables that reflect geometrical distortion, and find these to be effective in describing the contribution of chain conformation to the emission spectrum. The collective variables are also shown to be effective in describing the bond relaxation dynamics after photoexcitation. Such a relaxation is found to occur in approximately 100 fs and is guided by a compensatory release of energy between the double and single bonds in the vinylene junctions and p-phenyl rings. Finally, we find that the chain has a very slight preference for a more planar conformation in the excited state, compared to the ground state. However, the thermal motions induce the chain to explore out-of-plane conformations in both the ground and the excited states with an amplitude significantly greater than this difference.     

Ultrafast dynamical localization of photoexcited states in conformationally disordered poly(p-phenylenevinylene)

We consider two types of ultrafast dynamical localization of photoexcited states in conformationally disordered poly(p-phenylenevinylene). First, we discuss nonadiabatic interconversion from higher energy extended exciton states to lower energy more localized local exciton ground states. Second, we calculate the dynamics of local exciton ground states on their Born-Oppenheimer potential energy surfaces. We show that within the first C-C bond oscillation following photoexcitation (～35 fs) the exciton becomes self-trapped and localized over approximately eight monomers. This process is associated with a Calderia-Leggett type loss of phase coherence owing to the coupling of the polymer to a dissipative environment. Subsequent torsional relaxation (on a time scale of approximately picoseconds) has little effect on the localization. We conclude from this that the initial torsional disorder determines the spatial distribution and localization length of vertical excitations but that electron-phonon coupling is largely responsible for the localization length of self-trapped excitons. We next consider the effect of dynamical localization on fluorescence depolarization. We show that exciting higher energy states causes a larger fluorescence depolarization, because these states have a larger initial delocalization. Using the observation that fluorescence depolarization is a function of excitation wavelength and polymer conformation, we show how the models of exciton localization discussed here can be experimentally investigated.     

Temperature effects on femtosecond transient absorption kinetics of semiconducting single-walled carbon nanotubes

We report femtosecond transient absorption kinetics measured for selected semiconducting single-walled carbon nanotubes at different temperatures between 77 and 290 K. The nanotubes are embedded in a thin polymethylmethacrylate film, and the dominance of individual species enabled to probe selectively the kinetics associated with two desired tube types, the (6,5) and (7,5) tubes. A strikingly similar temperature dependence is found between the maximum change in the amplitude of transient absorption kinetics, the overall decay time and steady-state fluorescence emission intensity. The simplest explanation for our data is that the temperature dependence of the fluorescence intensity and the exciton decay kinetics are dominated by nonradiative decay and that the radiative decay rate is weakly temperature dependent.     

Temperature dependent exciton emission from herringbone aggregates of conjugated oligomers

In this work, the effect of temperature, exciton bandwidth, and size on the photoluminescence spectra of defect-free two-dimensional herringbone aggregates of pi-conjugated oligomers such as oligophenylene vinylene and oligothiophene is investigated theoretically. The model is based on exciton-phonon coupling in two-dimensional herringbone lattices with the exciton deriving from the lowest optical (1Ag-->1Bu) transition and the phonon from the most strongly coupled intramolecular vibrational mode with frequency omega0. Simple analytical expressions are obtained for the line strengths of the emission origin (0-0) and first replica (0-1) as a function of the number of molecules comprising the aggregate, N, the free exciton bandwidth, WD, and the temperature, T. At a given temperature, the 0-0 emission intensity initially scales as N/Nth, where Nth is the superradiant threshold number, but eventually converges to NT/Nth, where NT is the size independent thermal coherence number. NT is inversely proportional to temperature and proportional to the exciton band curvature (omegac) near the band bottom; NT=1+4piomegac/kbT. In striking contrast, the 0-1 line strength is relatively insensitive to temperature and size, but scales as the inverse square of WD+omega0. The insensitivity of the first replica to the exciton coherence number makes the ratio of the 0-0 to 0-1 line strengths a measure of the exciton coherence number. The ratio can be used to test for crystal purity. Comparison to experiments on thin films of quaterthiophene shows that the thermal coherence size is given by NT approximately 1+450/T (K) and that superradiance, which requires NT>Nth, can only be observed at temperatures less than 1 K.     

Temperature dependence of solvation dynamics of probe molecules in methanol-doped ice and in liquid ethanol

We have studied the solvation statics and dynamics of coumarin 343 and a strong photoacid (pK* approximately 0.7) 2-naphthol-6, 8-disulfonate (2N68DS) in methanol-doped ice (1% molar concentration of methanol) and in cold liquid ethanol in the temperature range of 160-270 K. Both probe molecules show a relatively fast solvation dynamics in ice, ranging from a few tens of picoseconds at about 240 K to nanoseconds at about 160 K. At about 160 K in doped ice, we observe a sharp decrease of the dynamic Stokes shift of both coumarin 343 and 2N68DS. Its value is approximately only 200 cm-1 at approximately 160 K compared to about 1100 cm-1 at T >/= 200 K (at times longer than t > 10 ps). We find a good correlation between the inefficient and slow excited-state proton-transfer rate at low-temperature ice, T < 180 K, and the dramatic decrease of the solvation energy, as measured by the dynamic band shift, at these low temperatures. We find that the average solvation rate in ice is similar to its value in liquid ethanol at all given temperatures in the range of 200-250 K. The surprisingly fast solvation rate in ice is explained by the relatively large freedom of the water hydrogen rotation in ice Ih.     

Slow geminate‐charge‐pair recombination dynamics at polymer: Fullerene heterojunctions in efficient organic solar cells

We explore charge recombination dynamics at electron donor‐acceptor heterojunctions, formed between a semiconductor polymer (PCDTBT) and a fullerene derivative (PC₇₀BM), by means of combined time‐resolved photoluminescence and transient absorption spectroscopies. Following prompt exciton dissociation across the heterojunction, a subset of bound electron‐hole pairs recombines with a temperature‐independent rate distribution spanning submicrosecond timescales to produce luminescent charge‐transfer excitons (CTX). At 14 K, this slow mechanism is the dominant geminate charge recombination pathway, whereas we also observe CTX emission on subnanosecond timescales at 293 K. We thus find that at these temperatures, a fraction of the initial charge‐pair population is trapped deeply such that they only recombine slowly over a broad distribution of timescales by quantum tunneling. We identify geminate polaron pairs (GPP) as a reservoir of long‐lived localized states that repopulate the CTX up to microsecond timescales. The observation of such distributed geminate‐charge recombination highlights the importance of the molecular nature of specific donor–acceptor electronic interactions in defining the relaxation pathways of trapped GPP. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Energy transfer in unsymmetrical phenylene ethynylene dendrimers

We have applied the fluorescence upconversion technique to explore the electronic excitation energy transfer in unsymmetrical phenylene ethynylene dendrimers. Steady-state emission spectra show that the energy transfer from the dendrons to the core is highly efficient. Ultrafast time-resolved fluorescence measurements are performed at various excitation wavelengths to explore the possibility of assigning absorption band structures to exciton localizations. We propose a kinetic model to describe the time-resolved data. Independent of the excitation wavelength, a typical rise-time value of 500 fs is measured for the fluorescence in the dendrimer without an energy trap, indicating initial delocalized excitation. While absorption is into delocalized exciton states, emission occurs from localized states. When an energy trap such as perylene is introduced on the dendrimer, varying the excitation wavelength yields different energy-transfer rates, and the excitation energy migrates to the trap through two channels. The interaction energy between the dendrimer backbone and the trap is estimated to be 75 cm(-1). This value is small compared to the vibronic bandwidth of the dendrimer, indicating that the monodendrons and the energy trap are weakly coupled.     

Time- and polarization-resolved optical spectroscopy of colloidal CdSe nanocrystal quantum dots in high magnetic fields

In an effort to elucidate the spin (rather than charge) degrees of freedom in colloidal semiconductor nanocrystal quantum dots, we report on a series of static and time-resolved photoluminescence measurements of colloidal CdSe quantum dots in ultrahigh magnetic fields up to 45 T. At low temperatures (1.5-40 K), the steady-state photoluminescence (PL) develops a high degree of circular polarization with applied magnetic field, indicating the presence of spin-polarized excitons. Time-resolved PL studies reveal a marked decrease in radiative exciton lifetime with increasing magnetic field and temperature. Except for an initial burst of unpolarized PL immediately following photoexcitation, high-field time-resolved PL measurements reveal a constant degree of circular polarization throughout the entire exciton lifetime, even in the presence of pronounced exciton transfer via F?rster energy transfer processes.     

Fluorescence spectra of naphthalene-perdeuteronaphthalene mixed crystals - energy transfer via guest excitons

The fluorescence spectra of the mixed crystal system naphthalene in perdeuteronaphthalene at concentrations between 0.1 and 50% have been measured with high spectral resolution. Up to 10% the spectra are superpositions of the spectra of monomers, pairs, trimers and some higher aggregates. The relative intensities of these individual aggregate spectra given evidence for trap to trap energy transfer without thermal excitation into the host exciton band. The monomers as the most abundant traps form a dilute exciton band 50 cm^?1 below the host band. By thermal activation into this dilute band energy is transferred between the aggregate states. In the 50% crystal emission from a mixed guest-host exciton band without individual clusters is observed.     

Localization and coherent dynamics of excitons in the two-dimensional optical spectrum of molecular J-aggregates

Two-dimensional optical spectra of J-aggregates at low temperature provide a large amount of information about the nature and dynamics of exciton states that is hidden in conventional broad band pump-probe spectra. By using numerical simulations, we study the two-dimensional absorption spectrum and find that it is dominated by a V-shaped negative peak and a blueshifted elliptic positive peak. We demonstrate a simple method to derive the energy dependence of the exciton localization size from the distance between these two features in the zero waiting time experiment. When the waiting time is turned on, the V peak is filled with an extra positive peak resulting from population relaxation. From the time evolution of this peak, energy dependent relaxation rates can be obtained. The oscillations of coherent contributions to the two-dimensional spectrum are not damped by inhomogeneous mechanisms and can be seen clearly.     

Absorption,fluorescence and stimulated fluorescence by polaritons in thin anthracene crystals. A re-interpretation of spectroscopic properties of anthracene

The transmission, absorption (excitation spectra) and fluorescence spectra of thin (? 47 nm) free mounted anthracene flakes have been measured. True absorption in b polarization in the region of the lowest exciton state occurs as a result of scattering by phonons. It has a minimum near the transverse exciton frequency and a maximum near the longitudinal exciton frequency, in agreement with expected polariton behaviour. Thickness dependent polariton states have finite absorption and fluorescence transition probabilities (due to crystal inhomogeneities) and are observed below the transverse exciton frequency. These polariton states represent the energy reservoir for excitation energy in the bulk of the crystal. A surface-induced exciton state is the origin of the sharp line fluorescence from pure crystals and accounts for the high efficiency of stimulated fluorescence at low temperatures. Stimulated fluorescence can also be observed from the polariton modes when excitation occurs in these modes. Resonance interactions between polariton modes and impurity levels represent an important pathway for fluorescence quenching in crystalline anthracene.     

Ultrafast exciton transfers in DNA and its nonlinear optical spectroscopy

We have calculated the nonlinear response function of a DNA duplex helix including the contributions from the exciton population and coherence transfers by developing an appropriate exciton theory as well as by utilizing a projector operator technique. As a representative example of DNA double helices, the B-form (dA)10-(dT)10 is considered in detail. The Green functions of the exciton population and coherence transfer processes were obtained by developing the DNA exciton Hamiltonian. This enables us to study the dynamic properties of the solvent relaxation and exciton transfers. The spectral density describing the DNA base-solvent interactions was obtained by adjusting the solvent reorganization energy to reproduce the absorption and steady-state fluorescence spectra. The time-dependent fluorescence shift of the model DNA system is found to be ultrafast and it is largely determined by the exciton population transfer processes. It is further shown that the nonlinear optical spectroscopic techniques such as photon echo peak shift and two-dimensional photon echo can provide important information on the exciton dynamics of the DNA double helix. We have found that the exciton-exciton coherence transfer plays critical roles in the peculiar energy transfer and ultrafast memory loss of the initially created excitonic state in the DNA duplex helix.     

On low temperature fluorescence of perylene crystals

At low temperatures, the broad excimer fluorescence band of α-perylene crystals is replaced by a weakly structured emission at higher energy. This emission originates from a new crystal state (Y-state) which is populated independently of the high temperature excimer (E-state). Due to the temperature dependence of its first order decay rate and due to the thermally activated formation of the E-state, the Y-emission grows rapidly at temperatures below 90 K. The Y-emission differs from the fluorescence of the monomeric β-perylene at 5.5 K by its Stokes shift of 1300 cm^?1, the lack of vibronic structure, the long first order decay time of 40 ns and the absence of bimolecular annihilation indicating a localized state. The Y-state is attributed to a less relaxed pair state formed upon contraction of the dimeric crystal lattice.     

Intramolecular charge transfer assisted by conformational changes in the excited state of fluorene-dibenzothiophene-S,S-dioxide co-oligomers

The strong solvatochromism observed for two fluorene-dibenzothiophene-S,S-dioxide oligomers in polar solvents has been investigated using steady-state and time-resolved fluorescence techniques. A low-energy absorption band, attributed to a charge-transfer (CT) state, is identified by its red shift with increasing solvent polarity. In nonpolar solvents, the emission of these conjugated luminescent oligomers shows narrow and well-resolved features, suggesting that the emission comes from a local excited state (LE), by analogy to their conjugated fluorene-based polymer counterparts. However, in polar solvents, only a featureless broad emission is observed at longer wavelengths (CT emission). A linear correlation between the energy maximum of the fluorescence emission and the solvent orientation polarizability factor Deltaf (Lippert-Mataga equation) is observed through a large range of solvents. In ethanol, below 230 K, the emission spectra of both oligomers show dual fluorescence (LE-like and CT) with the observation of a red-edge excitation effect. The stabilization of the CT emissive state by solvent polarity is accompanied/followed by structural changes to adapt the molecular structure to the new electronic density distribution. In ethanol, above 220 K, the solvent reorganization occurs on a faster time scale (less than 10 ps at 290 K), and the structural relaxation of the molecule (CT(unrelaxed) --> CT(Relaxed)) can be followed independently. The magnitude of the forward rate constant, k(1)(20 degrees C) approximately 20 x 10(9) s(-1), and the reaction energy barrier, E(a) approximately 3.9 kcal mol(-1), close to the energy barrier for viscous flow in ethanol (3.54 kcal mol(-1)), show that large-amplitude molecular motions are present in the stabilization of the CT state.     

Energy transfer via guest excitons in isotopic mixed naphthalene crystals

The temperature dependence of the fluorescence spectra of aggregates in naphthalene-perdeuteronaphthalene mixed crystals has been investigated between 1.4 and 70 K and for concentrations up to 50% naphthalene. It is shown that the most abundant traps — the monomer guest molecules — transfer energy like a guest exciton band 48 cm^?1 below the host exciton band. With increasing temperature, the excitation energy is redistributed between the different aggregate traps by thermal activation into the monomer states. The energy transfer constant within the monomer exciton band is measured as a function of concentration. It is suggested that dipole-dipole interaction between the monomer guests is responsible for the energy transfer via guest excitons.     

Manipulating exciton dynamics of thermally activated delayed fluorescence materials for tuning two-photon nanotheranostics

Rational manipulation of energy utilization from excited-state radiation of theranostic agents with a donor–acceptor structure is relatively unexplored. Herein, we present an effective strategy to tune the exciton dynamics of radiative excited state decay for augmenting two-photon nanotheranostics. As a proof of concept, two thermally activated delayed fluorescence (TADF) molecules with different electron-donating segments are engineered, which possess donor–acceptor structures and strong emissions in the deep-red region with aggregation-induced emission characteristics. Molecular simulations demonstrate that change of the electron-donating sections could effectively regulate the singlet–triplet energy gap and oscillator strength, which promises efficient energy flow. A two-photon laser with great permeability is used to excite TADF NPs to perform as theranostic agents with singlet oxygen generation and fluorescence imaging. These unique performances enable the proposed TADF emitters to exhibit tailored balances between two-photon singlet oxygen generation and fluorescence emission. This result demonstrates that TADF emitters can be rationally designed as superior candidates for nanotheranostic agents by the custom controlling exciton dynamics.

Exciton dynamics can be manipulated rationally in the design of TADF materials for nanotheranostics. Regulating the ΔE_ST and f promises efficient energy flow for tailoring balances between singlet oxygen generation and fluorescence emission.     

Recombination dynamics of CdTe/CdS core-shell nanocrystals

The recombination dynamics of zinc-blende-type, deep-red emitting CdTe/CdS core-shell nanocrystals is studied over a wide temperature range. Two characteristic decay regimes are found: a temperature-dependent decay component of a few nanoseconds and a long-living temperature-independent component of approximately 315 ns. The average decay time of the exciton states changes from 20 to 5ns when the temperature is increased from 15 to 295 K. At low temperatures, the observed decay behavior is assigned to thermally induced population and decay of the allowed exchange-split exciton states. At temperatures above T>100 K, nonradiative decay channels involving phonons start to contribute to the exciton recombination. The observed broad distribution in decay times, monitored by stretched exponential fitting functions, we explain by variations in the electron-hole overlap caused by a partly incomplete CdTe/CdS core-shell structure and the nearly energy-degenerated bright and dark state superposition.     

Amplified quenching of a conjugated polyelectrolyte by cyanine dyes

The conjugated polyelectrolyte PPESO3 features a poly(phenylene ethynylene) backbone substituted with anionic 3-sulfonatopropyloxy groups. PPESO3 is quenched very efficiently (KSV > 10(6) M(-1)) by cationic energy transfer quenchers in an amplified quenching process. In the present investigation, steady-state and picosecond time-resolved fluorescence spectroscopy are used to examine amplified quenching of PPESO3 by a series of cyanine dyes via singlet-singlet energy transfer. The goal of this work is to understand the mechanism of amplified quenching and to characterize important parameters that govern the amplification process. Steady-state fluorescence quenching of PPESO3 by three cationic oxacarbocyanine dyes in methanol solution shows that the quenching efficiency does not correlate with the Forster radius computed from spectral overlap of the PPESO3 fluorescence with the cyanines' absorption. The quenching efficiency is controlled by the stability of the polymer-dye association complex. When quenching studies are carried out in water where PPESO3 is aggregated, changes observed in the absorption and fluorescence spectra of 1,1',3,3,3',3'-hexamethylindotricarbocyanine iodide (HMIDC) indicate that the polymer templates the formation of a J-aggregate of the dye. The fluorescence dynamics in the PPESO3/HMIDC system were probed by time-resolved upconversion and the results show that PPESO3 to HMIDC energy transfer occurs on two distinctive time scales. At low HMIDC concentration, the dynamics are dominated by an energy transfer pathway with a time scale faster than 4 ps. With increasing HMIDC concentration, an energy pathway with a time scale of 0.1-1 ns is active. The prompt pathway (tau < 4 ps) is attributed to quenching of delocalized PPESO3 excitons created near the HMIDC association site, whereas the slow phase is attributed to intra- and interchain exciton diffusion to the HMIDC.