Triplet Recombination Research Articles

Molecular Packing Effects on the Optical Spectra and Triplet Dynamics in Oligofluorene Films

We report on the triplet spectra and dynamics in two types of oligomeric films deposited by two different techniques: thermal evaporation and spin coating. The different molecular arrangement in both films is manifested in a red shift of the absorption, PL, and T1-Tn absorption spectra of the sublimated film relative to the spin-coated one. Triplet recombination dynamics studied with steady-state photoinduced absorption (PA) spectroscopy follow a dispersive bimolecular recombination model away from the trap filling regime. We obtained values for the triplet bimolecular recombination ratio (beta) of 3.4 x 10 (-14) and 1.1 x 10 (-15) cm3 s (-1) for evaporated and spin-coated film, respectively, the difference being attributed to diverse molecular arrangement in both films.

Biradicals by triplet recombination of radical ion pairs

Radical ion pairs generated by photoinduced electron transfer may undergo return electron transfer (RET) in pairs of singlet or triplet multiplicity. RET efficiencies are determined by the free energy of RET and the topologies of the potential surfaces of parent molecule, radical ion and triplet state. If radical ion geometries are different from the corresponding triplet states, RET occurs either with cleavage ("dissociative" RET; 1,2-diphenylcyclopropane radical cations) or formation of C-C bonds ("associative" RET; norbornadiene radical cation). Radical ions of some strained ring compounds spontaneously undergo ring-opening; RET to such species form ring-opened triplets without major geometry changes. CIDNP spectroscopy offers unique insights into triplet RET.

Chlorophyll triplet states associated with Photosystem I and Photosystem II in thylakoids of the green alga Chlamydomonas reinhardtii

The analysis of FDMR spectra, recorded at multiple emission wavelengths, by a global decomposition technique, has allowed us to characterise the triplet populations associated with Photosystem I and Photosystem II of thylakoids in the green alga Chlamydomonas reinhardtii. Three triplet populations are observed at fluorescence emissions characteristic of Photosystem II, and their zero field splitting parameters have been determined. These are similar to the zero field parameters for the three Photosystem II triplets previously reported for spinach thylakoids, suggesting that they have a widespread occurrence in nature. None of these triplets have the zero field splitting parameters characteristic of the Photosystem II recombination triplet observed only under reducing conditions. Because these triplets are generated under non-reducing redox conditions, when the recombination triplet is undetectable, it is suggested that they may be involved in the photoinhibition of Photosystem II. At emission wavelengths characteristic of Photosystem I, three triplet populations are observed, two of which are attributed to the P 700 recombination triplet frozen in two different conformations, based on the microwave-induced fluorescence emission spectra and the triplet minus singlet difference spectra. The third triplet population detected at Photosystem I emission wavelengths, which was previously unresolved, is proposed to originate from the antenna chlorophyll of the core or the unusually blue-shifted outer antenna complexes of this organism.

The inter-relationship between triplet energies and spin chemistry

Triplet energies play a considerable role in optical spectroscopy, and can be determined from phosphorescence or the quenching thereof. Their role in spin chemistry may not be as obvious, but the triplet state has always had an important function or utility, namely of reaction intermediates such as radical pairs, their precursors, of carbenes, and of the final products. In situ NMR spectroscopy represents a useful tool to explore certain properties of the triplet state, especially in cases with no phosphorescence. The 'phase' of CIDNP resonances, i.e., emission or enhanced absorption, reflects the spin selectivity of electron transfer reactions. In radical ion pairs the spin selectivity is determined by the relation between the change of the standard free enthalpy DeltaG degrees during the electron back transfer and the triplet energies (E(T)) of the products. If triplet recombination is energetically feasible (DeltaG degrees > E(T)), it is typically the more efficient process in agreement with the Marcus theory.

Femtosecond ground state recovery: Measuring the intersystem crossing yield of polyspirobifluorene

Measurement of the quantum yield of triplet formation has been made for the prototypical conjugated polymer polyspirobifluorene in solution and solid state. An updated method has been described based on femtosecond time resolved ground state recovery following photoexcitation of the polymer. The two components to the recovery of the ground state due to the decay of the singlet and triplet excited states are clearly visible and from these it is possible to calculate Phi(T)=0.05+/-0.01 in solution, this gives k(isc)=5.4 x 10(7) s(-1) which compares favorably with other conjugated polymers. In polymer films an increased triplet yield of Phi(T)=0.12+/-0.02 is found to be independent of temperature, the increased yield is attributed to triplet recombination from charged states.

Time-resolved EPR investigation of charge recombination to a triplet state in a carotene-diporphyrin triad

Photoinduced charge separation and recombination were investigated in a triad consisting of a carotenoid (C), a tetraarylporphyrin (P) and a tris(heptafluoropropyl)porphyrin (PF), C–P–PF, by means of time-resolved electron paramagnetic resonance. The electron transfer process was studied in a glass of 2-methyltetrahydrofuran at 10 K, in the crystalline phase at 150 K and in the liquid nematic phase of the uniaxial LC E-7 at 295 K, and in the nematic phase of the LC ZLI-1167 at 300 K. In all the different media and in the different phases, the molecular triad undergoes two-step photoinduced electron transfer, with the generation of a long-lived charge-separated state (C•+–P–), and charge recombination to the triplet state, localized in the carotene moiety 3C–P–PF. Low-temperature charge separation and triplet recombination are common features of both fullerene-based and diporphyrin molecular triads, proving that the large delocalized π-electron system of the porphyrin electron acceptor leads to low total reorganization energy and low sensitivity to solvent stabilization of the radical ions in a similar way as for fullerene systems.

Double-Channel Contact Recombination of Radical Pairs Subjected to Spin Conversion via the Δg Mechanism

The contact recombination from both singlet and triplet states of a radical pair is studied assuming that the spin conversion is carried out by the fast transversal relaxation and Delta g mechanism. The alternative HFI mechanism is neglected as being much weaker in rather large magnetic fields. The magnetic-field-dependent quantum yields of the singlet and triplet recombination products, as well as of the free radical production, are calculated for any initial spin state and arbitrary separation of radicals in a pair. The magnetic field effect is traced and its diffusional (viscosity) dependence is specified.

Electronic Coupling Effects on Photoinduced Electron Transfer in Carotene−Porphyrin−Fullerene Triads Detected by Time-Resolved EPR

Photoinduced charge separation and recombination in a carotenoid-porphyrin-fullerene triad C-P-C60 (Bahr et al., 2000) have been followed by time-resolved electron paramagnetic resonance. The electron-transfer process has been characterized in a glass of 2-methyltetrahydrofuran and in the nematic phase of two uniaxial liquid crystals (E-7 and ZLI-1167). In all the different media, the molecular triad undergoes two-step photoinduced electron transfer, with the generation of a long-lived charge-separated state (C*+-P-C60*-), and charge recombination to the triplet state, localized in the carotene moiety, mimicking different aspects of the photosynthetic electron-transfer process. The magnetic interaction parameters have been evaluated by simulation of the spin-polarized radical pair spectrum. The weak exchange interaction parameter (J = +1.7 +/- 0.1 G) provides a direct measure of the dominant electronic coupling matrix element V between the C*+-P-C60*- radical pair state and the recombination triplet state 3C-P-C60. Comparison of the estimated values of V for this triad and a structurally related triad differing only in the porphyrin bridge (octaalkylporphyrin vs tetraarylporphyrin) explains in terms of an electronic coupling effect the approximately 6-fold variation of the recombination rate induced by the modification of the porphyrin bridge as derived by kinetic experiments (Bahr et al., 2000).

Electron Spin Dynamics as a Probe of Molecular Dynamics: Temperature-Dependent Magnetic Field Effects on Charge Recombination within a Covalent Radical Ion Pair

The electron spin-spin exchange interaction, 2J, in radical pairs (RPs) is exquisitely sensitive to the details of molecular structure and can thus serve as an important probe of structural dynamics in RPs of potential interest to photonic and electronic devices. Photoinitiated ultrafast two-step charge separation produces (1)(MeOAn(+)(*)-6ANI-NI(-)(*)), where MeOAn = p-methoxyaniline, 6ANI = 4-(N-piperidinyl)naphthalene-1,8-dicarboximide, and NI = naphthalene-1,8:4,5-bis(dicarboximide). Radical pair intersystem crossing subsequently produces (3)(MeOAn(+)(*)-6ANI-NI(-)(*)), and the total RP population decays with approximately 10 ns lifetime at 140 K, which increases to nearly 30 ns at 300 K in toluene. The activation energy observed for this process is negative and can be explained by a mechanism involving a conformational preequilibrium of the RP followed by charge recombination. Over the same temperature range, the magnetic field effect (MFE) on yield of the triplet recombination product, MeOAn-6ANI-(3)()NI, yields the magnitude of 2J, which directly monitors the superexchange electronic coupling for charge recombination. A single resonance in the MFE plot is observed at 300 K, which splits into two resonances at temperatures below 230 K, suggesting that there are two distinct groups of RP conformations at low temperature. The magnitude of 2J for the lower field resonance (10 mT) at 140 K is 5 times smaller than that of the high field resonance. At 300 K the equilibrium is shifted almost entirely to the set of conformers with the stronger electronic coupling. The motion that couples these two groups of conformations is the motion that most effectively gates the donor-acceptor electronic coupling.

Triplet recombination at Pb centers and its implications for capture cross sections

Pulsed electrically detected magnetic resonance measurements are presented showing that Pb centers at the crystalline silicon (c-Si) (111) to silicon dioxide (SiO2) interface can cause recombination of strongly coupled spin pairs in singlet and triplet configurations. The implication of these findings is that two different electron capture cross sections can exist at a single defect. This shows that the previously observed two capture cross sections at the c-Si∕SiO2 interface do not necessarily imply the existence of additional non-Pb-like centers such as oxygen-backbonded silicon dangling bonds.

Photochemistry of Artificial Photosynthetic Reaction Centers in Liquid Crystals Probed by Multifrequency EPR (9.5 and 95 GHz)

Photoinduced charge separation and recombination in a carotenoid-porphyrin-fullerene triad C-P-C(60)(1) have been followed by multifrequency time-resolved electron paramagnetic resonance (TREPR) at intermediate magnetic field and microwave frequency (X-band) and high field and frequency (W-band). The electron-transfer process has been characterized in the different phases of two uniaxial liquid crystals (E-7 and ZLI-1167). The triad undergoes photoinduced electron transfer, with the generation of a long-lived charge-separated state, and charge recombination to the triplet state, localized in the carotene moiety, mimicking different aspects of the photosynthetic electron-transfer process. Both the photoinduced spin-correlated radical pair and the spin-polarized recombination triplet are observed starting from the crystalline up to the isotropic phase of the liquid crystals. The W-band TREPR radical pair spectrum has allowed unambiguous assignment of the spin-correlated radical pair spectrum to the charge-separated state C(.+)-P-C(60)(.-). The magnetic interaction parameters have been evaluated by simulation of the spin-polarized radical pair spectrum and the spin-selective recombination rates have been derived from the time dependence of the spectrum. The weak exchange interaction parameter (J = +0.5 +/- 0.2 G) provides a direct measure of the dominant electronic coupling matrix element V between the C(.+)-P-C(60)(.-) radical pair state and the recombination triplet state (3)C-P-C(60). The kinetic parameters have been analyzed in terms of the effect of the liquid crystal medium on the electron-transfer process. Effects of orientation of the molecular triad in the liquid crystal are evidenced by simulations of the carotenoid triplet state EPR spectra at different orientations of the external magnetic field with respect to the director of the mesophase. The order parameter (S = 0.5 +/- 0.05) has been evaluated.

Making a molecular wire: charge and spin transport through para-phenylene oligomers.

Functional molecular wires are essential for the development of molecular electronics. Charge transport through molecules occurs primarily by means of two mechanisms, coherent superexchange and incoherent charge hopping. Rates of charge transport through molecules in which superexchange dominates decrease approximately exponentially with distance, which precludes using these molecules as effective molecular wires. In contrast, charge transport rates through molecules in which incoherent charge hopping prevails should display nearly distance independent, wirelike behavior. We are now able to determine how each mechanism contributes to the overall charge transport characteristics of a donor-bridge-acceptor (D-B-A) system, where D = phenothiazine (PTZ), B = p-oligophenylene, and A = perylene-3,4:9,10-bis(dicarboximide) (PDI), by measuring the interaction between two unpaired spins within the system's charge separated state via magnetic field effects on the yield of radical pair and triplet recombination product.

Theory of time-domain measurement of spin-dependent recombination with pulsed electrically detected magnetic resonance

The theoretical foundations of the time domain measurement of spin-dependent charge carrier recombination by means of pulsed electrically detected magnetic resonance (EDMR) are outlined. Pulsed EDMR is based on the transient measurement of electrical currents in semiconductors after a coherent manipulation of paramagnetic centers with pulsed electron spin resonance (ESR). A model of spin-dependent recombination is introduced combining features of previous models into one general picture that takes influences by spin-relaxation, singlet and triplet recombination as well as spin-spin interactions within recombining charge carrier pairs into account. Based thereon, predictions for excess charge carrier currents after short coherent pulse ESR excitations are made which show that spin coherence in semiconductors can be observed by means of current measurements and hence, microscopic, quantitative information about charge carrier recombination dynamics by means of pulsed EDMR is attainable.

Analysis of photosystem II triplet states in thylakoids by fluorescence detected magnetic resonance in relation to the redox state of the primary quinone acceptor QA

The dependence of PSII triplet populations as a function of the primary quinone acceptor Q A redox state has been investigated by means of the fluorescence detected magnetic resonance (FDMR) technique in isolated thylakoid membranes. The results show that the population level of a microsecond decaying component having zero field splitting parameters | D |=0.0292 cm −1 and | E |=0.0037 cm −1 is inversely correlated to that of the recombination triplet (| D |=0.0285 cm −1 | E |=0.045 cm −1 ). The results could be interpreted in terms of the fast (50–150 μs) decaying population being either the recombination triplet when the primary quinone Q A is singly reduced or a triplet located on a chlorophyll which is in tight singlet transfer coupling with the primary donor.

Photosystem II single crystals studied by transient EPR: the light-induced triplet state

Transient electron paramagnetic resonance (TR EPR) at 9.8 GHz has been used to study the light-induced triplet state in single crystals of Photosystem II (PS II). The crystals were grown from a solution of PS II core complexes from the thermophilic cyanobacterium Synechococcus elongatus. The core complexes contain at least 17 subunits, including the water-oxidizing complex, and 32 chlorophyll a molecules per PS II complex. The PS II complexes are active in light-induced electron transfer and water oxidation. The crystals belong to the orthorhombic space group P2 12 12 1, with four dimers of PS II complexes per unit cell. Laser excitation was used to generate the recombination triplet state in PS II which was then studied by EPR at low temperatures (10 K). The crystal spectra show the same magnitude of the zero-field splitting (ZFS) values D, E as spectra obtained earlier for the triplet state of PS II in frozen solution. The orientation of the ZFS tensor D of the triplet state with respect to the crystallographic axes has been deduced from the analysis of angular-dependent EPR spectra. Knowledge of the orientation of the D tensor component perpendicular to the plane of the chlorophyll ( D Z ) allows an assignment on which chlorophyll of the reaction centre the triplet state is localized at low temperatures. Furthermore, the orientation of the D X and D Y components of the D tensor yielded the in-plane orientation of the respective chlorophyll in the reaction centre providing first experimental evidence for the orientation of this molecule in the PS II.

Using spin dynamics of covalently linked radical ion pairs to probe the impact of structural and energetic changes on charge recombination.

We have synthesized a series of structurally related, covalently linked electron donor-acceptor triads having highly restricted conformations to study the effects of radical ion pair (RP) structure, energetics, and solvation on charge recombination. The chromophoric electron acceptor in these triads is a 4-aminonaphthalene-1,8-dicarboximide (6ANI), in which the 4-amine nitrogen atom is part of a piperazine ring. The second nitrogen atom of the piperazine ring is part of a para-substituted aniline donor, where the para substituents are X = H, OMe, and NMe(2). The imide group of 6ANI is linked to a naphthalene-1,8:4,5-bis(dicarboximide) (NI) electron acceptor across a phenyl spacer in a meta relationship. The triads undergo two-step photoinduced electron transfer to yield their respective XAn(*)(+)-6ANI-Ph-NI(*)(-) RP states, which undergo radical pair intersystem crossing followed by charge recombination to yield (3)NI. Time-resolved electron paramagnetic resonance experiments on the spin-polarized RPs and triplet states carried out in toluene and in E-7, a mixture of nematic liquid crystals (LCs), show that for all three triads, the XAn(*)(+)-6ANI-Ph-NI(*)(-) RPs are correlated radical pairs and directly yield values of the spin-spin exchange interaction, J, and the dipolar interaction, D. The values of J are all about -1 mT and show that the LC environment most likely enforces the chair conformation at the piperazine ring, for which the RP distance is larger than that for the corresponding boat conformation. The values of D yield effective RP distances that agree well with those calculated earlier from the spin distributions of the radical ions. Within the LC, changing the temperature shows that the CR mechanism can be changed significantly as the energy levels of the RPs change relative to that of the recombination triplet.

Delayed fluorescence of a poly (p-phenylenevinylene) derivative: Triplet–triplet annihilation versus geminate pair recombination

The question of the origin of delayed fluorescence from a phenyl-substituted poly(p-phenylenevinylene)-type copolymer (Ph-PPV) is addressed. Two origins have to be considered, i.e., triplet–triplet annihilation and recombination of geminate electron–hole pairs. Ph-PPV is investigated in the form of two different samples, namely diluted in 2-methyltetrahydrofuran (MTHF) glass at 80 K and as a thin film of optical density of 0.6. It will be shown that in the diluted solution, delayed fluorescence is due to triplet–triplet annihilation and in the thin film, it is due to geminate pair recombination. The assignment of delayed fluorescence to geminate pair recombination in the thin film could be made due to delayed fluorescence experiments under applying an electric field of 2×106 V/cm. The delayed fluorescence is strongly influenced by the electric field which is a sign that charged species, i.e., geminate electron–hole pairs, are involved in the process of delayed fluorescence.

Fluorescence and Absorption Detected Magnetic Resonance of Membranes from the Green Sulfur Bacterium Chlorobium limicola. Full Assignment of Detected Triplet States

Optically detected magnetic resonance of chlorosomes-containing membranes from the green sulfur bacterium Chlorobium limicola has been performed both by fluorescence and absorption detection. Triplet states localized in the chlorosomes and in the FMO complex have been characterized. After chemical reduction with dithionite followed by illumination at 200 K, a recombination triplet state localized in the primary donor P840 becomes populated under illumination at low temperature. A reaction center triplet state characterized by slightly different ZFS parameters, grows up irreversibly after prolonged illumination at low temperature in the presence of reductant. We were able to obtain the T−S spectra of the FMO complex and of the primary donor P840 in their native environment and to compare them to the spectra obtained in isolated complexes previously published, revealing differences in the spectra. Fluorescence detected magnetic resonance measurements demonstrate that the BChl c antenna pigments are connected via energy transfer to the BChl a molecules at the low temperature of the measurements (1.8 K) and that all the pigments carrying the triplet states are sensitive to the redox treatment. Dithionite reduction, in fact, induces an enhancement of the BChl c and, at a major extent, of the BChl a fluorescence yield accompanied by an increase of the yield of all the triplet states of the pigments. Evidence for the presence of BChl c excited states quenchers in the core chlorosome and for their selective effect at low temperature is provided, and the location of the quenchers close to BChl c molecules absorbing at longer wavelengths discussed.

Chlorophyll triplet states associated with photosystem II of thylakoids.

The analysis of FDMR thylakoid spectra, determined at multiple emission wavelengths, by a global decomposition technique, has revealed the presence of three previously undescribed triplet populations at emission wavelengths characteristic of Photosystem II chlorophyll/protein complexes. Their zero-field splitting parameters have been determined in order to compare them with the well-studied PSII recombination triplet state. None of these triplets have the zero-field splitting parameters characteristic of the recombination triplet and are therefore probably not generated directly in the reaction center. On the basis of their microwave-induced emission spectra, it is suggested that two are probably generated in the core complex(es) while the third may be generated in the external antenna. These triplets are formed under nonreducing redox conditions, when the recombination triplet is undetectable. It is suggested that they may be involved in the photoinhibitory damage of Photosystem II. The triplet-minus-singlet spectrum associated with the recombination triplet state has been determined for thylakoids after reduction of the secondary acceptors. Its main peak is at 685 nm, slightly red shifted with respect to earlier reports, with a weak signal, of opposite sign at approximately 675 nm. The 685 nm peak indicates that at cryogenic temperatures, the triplet is located on the long-wavelength chlorophyll state present in the reaction center complex of Photosystem II (D1.D2.Cytb(559) complex). From the absence of a clear structure in the 680 nm absorption region, this long-wavelength absorbing state does not appear to be strongly coupled to P(680), though it must be associated with one of the "inner core" pigments recently identified in the photosystem II crystallographic structure [Zouni et al. (2001) Nature 408, 739-743].

Light-intensity and temperature dependence of trap-dangling bond recombination in hydrogenated microcrystalline silicon

AbstractA quantitative study of the trap-dangling bond tunneling recombination in hydrogenated microcrystalline silicon (μc-Si:H) is presented. The transition coefficients were measured at various light exposures and temperatures between T = 10 K and T = 140 K using time-domain measurements of spin-dependent recombination (TSR). TSR is a new characterization method related to electrically detected magnetic resonance (EDMR). It combines the advantages of pulsed electron spin resonance with that of EDMR. In contrast to previous models, the experimental results can only be interpreted if the interaction between the spins of the trap and the dangling bonds as well as triplet recombination is considered.