Lifetime Shortening and Fast Energy‐Tansfer Processes upon Dimerization of a A‐π‐D‐π‐A Molecule

Time‐resolved fluorescence and transient absorption experiments uncover a distinct change in the relaxation dynamics of the homo‐dimer formed by two 2,5‐bis[1‐(4‐N‐methylpyridinium)ethen‐2‐yl)]‐N‐methylpyrrole ditriflate ( M ) units linked by a short alkyl chain when compared to that of the monomer M . Fluorescence decay traces reveal characteristic decay times of 1.1 ns and 210 ps for M and the dimer, respectively. Transient absorption spectra in the spectral range of 425–1050 nm display similar spectral features for both systems, but strongly differ in the characteristic relaxation times gathered from a global fit of the experimental data. To rationalize the data we propose that after excitation of the dimer the energy localizes on one M branch and then decays to a dark state, peculiar only of the dimer. This dark state relaxes to the ground state within 210 ps through non‐radiative relaxation. The nature of the dark state is discussed in relation to different possible photophysical processes such as excimer formation and charge transfer between the two M units. Anisotropy decay traces of the probe‐beam differential transmittance of M and the dimer fall on complete different time scales as well. The anisotropy decay for M is satisfactorily ascribed to rotational diffusion in DMSO, whereas for the dimer it occurs on a faster time scale and is likely caused by energy‐transfer processes between the two monomer M units.     

Optical coherence and theoretical study of the excitation dynamics of a highly symmetric cyclophane-linked oligophenylenevinylene dimer

Optoelectronic properties of a polyphenylenevinylene-based oligomer and its paracylophane-linked dimer are studied using a variety of experimental and theoretical techniques. Despite the symmetrical structure and redshifted absorption of the dimer versus the monomer, an exciton picture is not the most appropriate. Electronic structure calculations establish changes in charge density upon optical excitation and show localized excitations that cannot be accounted for by a simple Frenkel exciton model. Visible frequency pump-probe anisotropy measurements suggest that the dimer should be considered as a three-level system with a fast, approximately 130 fs, internal conversion from the higher to lower energy excited electronic state. Signatures of nuclear relaxation processes are compared for electric field-resolved transient grating and two-dimensional photon echo spectra. These measurements reveal that nuclear relaxation occurs on similar time scales for the monomer and dimer. The connection between the spectral phase of four-wave mixing signals and the time dependent width of a nuclear wave packet is discussed. Semiempirical electronic structure and metropolis Monte Carlo calculations show that the dominant line broadening mechanisms for the monomer and dimer are associated with inter-ring torsional coordinates. Together, the theoretical calculations and electric field-resolved four-wave mixing experiments suggest that while the structure of dimer is more rigid than that of monomer, the difference in their rigidities is not sufficient to slow down excited state relaxation of dimer with respect to the monomer.     

Excitation migration along oligophenylenevinylene-based chiral stacks: delocalization effects on transport dynamics

Atomistic models based on quantum-chemical calculations are combined with time-resolved spectroscopic investigations to explore the migration of electronic excitations along oligophenylenevinylene-based chiral stacks. It is found that the usual Pauli master equation (PME) approach relying on uncoherent transport between individual chromophores underestimates the excitation diffusion dynamics, monitored here by the time decay of the transient polarization anisotropy. A better agreement to experiment is achieved when accounting for excitation delocalization among acceptor molecules, as implemented in a modified version of the PME model. The same models are applied to study light harvesting and trapping in guest-host systems built from oligomers of different lengths.     

窄带系聚合物APFO3的激发态光物理特性

化学计算证实了光致激发窄带系聚合物APFO3后,会发生链内电荷转移（ICT）过程,同时这一特性还影响了吸收光谱中的第一吸收带. 瞬态吸收结果再一次表明了当聚合物在单分散体系中确实存在ICT特性,而且这种特性会同振动弛豫竞争. 在聚集态中,受链间相互作用的影响,ICT特性会消失,而且激子弛豫过程将在光致激发后的弛豫过程中占据主导地位. 混有PC61BM的APFO3薄膜的光致激发动力学显示,当PC61BM 的含量超过50%时,激子解离已经达到饱和. 基于此异质节的光伏器件性能显示PC61BM的含量高于50％以后,光电流的增幅也很小．     

On the doubly ionized states of Ar2 and their intra- and interatomic decay to Ar2 3+

Potential energy curves of the Auger state Ar+(2p(-1))-Ar, the different one- and two-site dicationic states Ar2 ++ (with energies in the range of 32-77 eV), and the lowest two-site tricationic states Ar++ - Ar+ (with energies in the range of 64-76 eV) computed using elaborated ab initio methods are reported. The accessible relaxation channels of the electronic states of Ar++ - Ar populated by Auger decay are studied. In particular, we study in detail the interatomic Coulombic decay following the population of one-site satellite states of Ar++(3s(-1)3p(-1))-Ar recently observed experimentally. Other relaxation pathways of Ar++ - Ar, including radiative charge transfer, nuclear dynamics through curve crossing, and intra-atomic decay processes are also investigated.     

A combined experimental and theoretical study on photoinduced intramolecular charge transfer in trans-ethyl p-(dimethylamino)cinamate

Intramolecular charge transfer (ICT) behavior of trans-ethyl p-(dimethylamino)cinamate (EDAC) in various solvents has been studied by steady-state absorption and emission, picosecond time-resolved fluorescence spectroscopy and femtosecond transient absorption experiments as well as time-dependent density functional theory (TDDFT). Large fluorescence spectral shift in more polar solvents indicates an efficient charge transfer from the donor site to the acceptor moiety in the excited state compared to the ground state. The energy for 0,0 transition (ν_0,0) for EDAC shows very good linear correlation with static solvent dielectric property. The relaxation dynamics of EDAC in the excited state can be effectively described by a “three state” model where, the locally excited (LE) state converts into the ICT state within 350 ± 100 fs. A combination of solvent reorganization and intramolecular vibrational relaxation within 0.5–6 ps populates the relaxed ICT state which undergoes fluorescence decay within few tens to hundreds of picoseconds.     

Femtosecond depolarization dynamics of tris(8-hydroxyquinoline) aluminum films

For vapor-deposited tris(8-hydroxyquinoline) aluminum thin films, steady-state and subpicosecond transient optical anisotropy are investigated. It is found that the transient absorption anisotropy decays within tens of picoseconds. With a simple model calculation, the excited state population and anisotropy decay dynamics are disentangled, and the latter signal, the depolarization of the excited state, is explained by the energy transfer between the non-orthogonally-coordinated quinolate ligands. It is also shown that there are two pathways for this fast interligand energy transfer.     

Influence of thermal fluctuations on interfacial electron transfer in functionalized TiO2 semiconductors

The influence of thermal fluctuations on the dynamics of interfacial electron transfer in sensitized TiO2-anatase semiconductors is investigated by combining ab initio DFT molecular dynamics simulations and quantum dynamics propagation of transient electronic excitations. It is shown that thermal nuclear fluctuations speed up the underlying interfacial electron transfer dynamics by introducing nonadiabatic transitions between electron acceptor states, localized in the vicinity of the photoexcited adsorbate, and delocalized states extended throughout the semiconductor material, creating additional relaxation pathways for carrier diffusion. Furthermore, it is shown that room-temperature thermal fluctuations reduce the anisotropic character of charge diffusion along different directions in the anatase crystal and make similar the rates for electron injection from adsorbate states of different character. The reported results are particularly relevant to the understanding of temperature effects on surface charge separation mechanisms in molecular-based photo-optic devices.     

Anti-correlated spectral motion in bisphthalocyanines: evidence for vibrational modulation of electronic mixing

We exploit a coherently excited nuclear wave packet to study nuclear motion modulation of electronic structure in a metal bridged phthalocyanine dimer, lutetium bisphthalocyanine, which displays two visible absorption bands. We find that the nuclear coordinate influences the energies of the underlying exciton and charge resonance states as well as their interaction; the interplay of the various couplings creates unusual anti-correlated spectral motion in the two bands. Excited state relaxation dynamics are the same regardless of which transition is pumped, with decay time constants of 1.5 and 11 ps. The dynamics are analyzed using a three-state kinetic model after relaxation from one or two additional states faster than the experimental time resolution of 50-100 fs.     

Intrachain energy migration to weak charge-transfer state in polyfluorene end-capped with naphthalimide derivative

Polyfluorene end-capped with N-(2-benzothiazole)-1,8-naphthalimide (PF-BNI) is a highly fluorescent material with fluorescence emission modulated by solvent polarity. Its low energy excited state is assigned as a mixed configuration state between the singlet S(1) of the fluorene backbone (F) with the charge transfer (CT) of the end group BNI. The triexponential fluorescence decays of PF-BNI were associated with fast energy migration to form an intrachain charge-transfer (ICCT) state, polyfluorene backbone decay, and ICCT deactivation. Time-resolved fluorescence anisotropy exhibited biexponential relaxation with a fast component of 12-16 ps in addition to a slow one in the range 0.8-1.4 ns depending on the solvent, showing that depolarization occurs from two different processes: energy migration to form the ICCT state and slow rotational diffusion motion of end segments at a longer time. Results from femtosecond transient absorption measurements agreed with anisotropy decay and showed a decay component of about 16 ps at 605 nm in PF-BNI ascribed to the conversion of S(1) to the ICCT excited state. From the ratio of asymptotic and initial amplitudes of the transient absorption measurement, the efficiency of intrachain ICCT formation is estimated in 0.5, which means that, on average, half of the excited state formed in a BNI-(F)(n)-BNI chain with n = 32 is converted to its low energy intrachain charge-transfer (ICCT) state.     

Solvent effects on the excited-state processes of protochlorophyllide: a femtosecond time-resolved absorption study

The excited-state dynamics of protochlorophyllide a, a porphyrin-like compound and, as substrate of the NADPH/protochlorophyllide oxidoreductase, a precursor of chlorophyll biosynthesis, is studied by femtosecond absorption spectroscopy in a variety of solvents, which were chosen to mimic different environmental conditions in the oxidoreductase complex. In the polar solvents methanol and acetonitrile, the excited-state dynamics differs significantly from that in the nonpolar solvent cyclohexane. In methanol and acetonitrile, the relaxation dynamics is multiexponential with three distinguishable time scales of 4.0-4.5 ps for vibrational relaxation and vibrational energy redistribution of the initially excited S1 state, 22-27 ps for the formation of an intermediate state, most likely with a charge transfer character, and 200 ps for the decay of this intermediate state back to the ground state. In the nonpolar solvent cyclohexane, only the 4.5 ps relaxational process can be observed, whereas the intermediate intramolecular charge transfer state is not populated any longer. In addition to polarity, solvent viscosity also affects the excited-state processes. Upon increasing the viscosity by adding up to 60% glycerol to a methanolic solution, a deceleration of the 4 and 22 ps decay rates from the values in pure methanol is found. Apparently not only vibrational cooling of the S1 excited state is slowed in the more viscous surrounding, but the formation rate of the intramolecular charge transfer state is also reduced, suggesting that nuclear motions along a reaction coordinate are involved in the charge transfer. The results of the present study further specify the model of the excited-state dynamics in protochlorophyllide a as recently suggested (Chem. Phys. Lett. 2004, 397, 110).     

Excited state proton transfer is not involved in the ultrafast deactivation of Guanine-Cytosine pair in solution

Different derivatives of Guanine (G) and Cytosine (C), which sterically enforce the Watson-Crick (WC) conformer, have been studied in CHCl(3) by means of broad-band transient absorption spectroscopy. Our experiments rule out the involvement of an Excited State Proton Transfer (ESPT), which dominates the excited state decay of GC in the gas phase. Instead, the ultrafast dynamics via internal conversion occurs in a polar environment mainly by relaxation in the monomer moieties. Time-dependent density functional theory (TD-DFT) calculations in solution indeed indicate that population transfer from the bright excited states toward the charge transfer state is not effective in CHCl(3) and a noticeable energy barrier is associated with the ESPT reaction. ESPT is therefore not expected to be a main deactivation route for GC pairs within DNA.     

Primary events in the blue light sensor plant cryptochrome: intraprotein electron and proton transfer revealed by femtosecond spectroscopy

Photoreceptors are chromoproteins that undergo fast conversion from dark to signaling states upon light absorption by the chromophore. The signaling state starts signal transduction in vivo and elicits a biological response. Therefore, photoreceptors are ideally suited for analysis of protein activation by time-resolved spectroscopy. We focus on plant cryptochromes which are blue light sensors regulating the development and daily rhythm of plants. The signaling state of these flavoproteins is the neutral radical of the flavin chromophore. It forms on the microsecond time scale after light absorption by the oxidized state. We apply here femtosecond broad-band transient absorption to early stages of signaling-state formation in a plant cryptochrome from the green alga Chlamydomonas reinhardtii. Transient spectra show (i) subpicosecond decay of flavin-stimulated emission and (ii) further decay of signal until 100 ps delay with nearly constant spectral shape. The first decay (i) monitors electron transfer from a nearby tryptophan to the flavin and occurs with a time constant of τ(ET) = 0.4 ps. The second decay (ii) is analyzed by spectral decomposition and occurs with a characteristic time constant τ(1) = 31 ps. We reason that hole transport through a tryptophan triad to the protein surface and partial deprotonation of tryptophan cation radical hide behind τ(1). These processes are probably governed by vibrational cooling. Spectral decomposition is used together with anisotropy to obtain the relative orientation of flavin and the final electron donor. This narrows the number of possible electron donors down to two tryptophans. Structural analysis suggests that a set of histidines surrounding the terminal tryptophan may act as proton acceptor and thereby stabilize the radical pair on a 100 ps time scale.     

Tuning Optical and Electron Donor Properties by Peripheral Thio–Aryl Substitution of Subphthalocyanine: A New Series of Donor–Acceptor Hybrids for Photoinduced Charge Separation

Subphthalocyanine (SubPc), a unique ring‐reduced member of the common phthalocyanines family, although known for its higher absorptivity, reveals narrow absorption with peak maxima around 570 nm thus limiting its utility in light‐energy‐harvesting applications. In the present study, by peripheral thio–aryl substitution of SubPc macrocycle, the spectral properties have been modulated to extend the absorption and emission well into the visible/near‐IR region. Additionally, for α‐ring‐substituted derivatives, facile oxidation of SubPc was witnessed, thus making these derivatives better electron donors. Next, the preparation of donor–acceptor dyads containing the well‐known electron acceptor C₆₀ connected to the central boron atom of SubPc was accomplished by making use of the 1,3‐dipolar cycloaddition reaction. Control experiments and free‐energy calculations using the redox and spectral data suggested that the observed fluorescence quenching of SubPc in these dyads is due to electron transfer. Accordingly, transient spectral studies performed both in polar and nonpolar solvents conclusively proved electron transfer to be the quenching mechanism in these dyads. The measured rate constants by fitting kinetic data revealed efficient charge separation and charge recombination processes, suggesting that these dyads could be useful materials for the construction of light‐to‐electricity or light‐to‐fuel production devices.     

Exciton coherence lifetimes from electronic structure

We model the coherent energy transfer of an electronic excitation within covalently linked aromatic homodimers from first-principles. Our results shed light on whether commonly used models of the bath calculated via detailed electronic structure calculations can reproduce the key dynamics. For the systems we model, the time scales of coherent transport are experimentally known from time-dependent polarization anisotropy measurements, and so we can directly assess whether current techniques are predictive for modeling coherent transport. The coupling of the electronic degrees of freedom to the nuclear degrees of freedom is calculated from first-principles rather than assumed, and the fluorescence anisotropy decay is directly reproduced. Surprisingly, we find that although time-dependent density functional theory absolute energies are routinely in error by orders of magnitude more than the coupling energy between monomers, the coherent transport properties of these dimers can be semi-quantitatively reproduced from these calculations. Future directions which must be pursued to yield predictive and reliable models of coherent transport are suggested.     

Crossover from superexchange to hopping as the mechanism for photoinduced charge transfer in DNA hairpin conjugates

The mechanism and dynamics of photoinduced charge separation and charge recombination have been investigated in synthetic DNA hairpins possessing donor and acceptor stilbenes separated by one to seven A:T base pairs. The application of femtosecond broadband pump-probe spectroscopy, nanosecond transient absorption spectroscopy, and picosecond fluorescence decay measurements permits detailed analysis of the formation and decay of the stilbene acceptor singlet state and of the charge-separated intermediates. When the donor and acceptor are separated by a single A:T base pair, charge separation occurs via a single-step superexchange mechanism. However, when the donor and acceptor are separated by two or more A:T base pairs, charge separation occurs via a multistep process consisting of hole injection, hole transport, and hole trapping. In such cases, hole arrival at the electron donor is slower than hole injection into the bridging A-tract. Rate constants for charge separation (hole arrival) and charge recombination are dependent upon the donor-acceptor distance; however, the rate constant for hole injection is independent of the donor-acceptor distance. The observation of crossover from a superexchange to a hopping mechanism provides a "missing link" in the analysis of DNA electron transfer and requires reevaluation of the existing literature for photoinduced electron transfer in DNA.     

Polarized pump-probe measurements of electronic motion via a conical intersection

Polarized femtosecond pump-probe spectroscopy is used to observe electronic wavepacket motion for vibrational wavepackets centered on a conical intersection. After excitation of a doubly degenerate electronic state in a square symmetric silicon naphthalocyanine molecule, electronic motions cause a approximately 100 fs drop in the polarization anisotropy that can be quantitatively predicted from vibrational quantum beat modulations of the pump-probe signal. Vibrational symmetries are determined from the polarization anisotropy of the vibrational quantum beats. The polarization anisotropy of the totally symmetric vibrational quantum beats shows that the electronic wavepackets equilibrate via the conical intersection within approximately 200 fs. The relationship used to predict the initial electronic polarization anisotropy decay from the asymmetric vibrational quantum beat amplitudes indicates that the initial width of the vibrational wavepacket determines the initial speed of electronic wavepacket motion. For chemically reactive conical intersections, which can have 1000 times greater stabilization energies than the one observed here, the same theory predicts electronic equilibration within 2 fs. Such electronic movements would be the fastest known chemical processes.     

Spin relaxation effects in photochemically induced dynamic nuclear polarization spectroscopy of nuclei with strongly anisotropic hyperfine couplings

We describe experimental results and theoretical models for nuclear and electron spin relaxation processes occurring during the evolution of 19F-labeled geminate radical pairs on a nanosecond time scale. In magnetic fields of over 10 T, electron-nucleus dipolar cross-relaxation and longitudinal DeltaHFC-Deltag (hyperfine coupling anisotropy--g-tensor anisotropy) cross-correlation are shown to be negligibly slow. The dominant relaxation process is transverse DeltaHFC-Deltag cross-correlation, which is shown to lead to an inversion in the geminate 19F chemically induced dynamic nuclear polarization (CIDNP) phase for sufficiently large rotational correlation times. This inversion has recently been observed experimentally and used as a probe of local mobility in partially denatured proteins (Khan, F.; et al. J. Am. Chem. Soc. 2006, 128, 10729-10737). The essential feature of the spin dynamics model employed here is the use of the complete spin state space and the complete relaxation superoperator. On the basis of the results reported, we recommend this approach for reliable treatment of magnetokinetic systems in which relaxation effects are important.