Two-photon-induced singlet fission in rubrene single crystal.

The two-photon-induced singlet fission was observed in rubrene single crystal and studied by use of femtosecond pump-probe spectroscopy. The location of two-photon excited states was obtained from the nondegenerate two-photon absorption (TPA) spectrum. Time evolution of the two-photon-induced transient absorption spectra reveals the direct singlet fission from the two-photon excited states. The TPA absorption coefficient of rubrene single crystal is 52 cm∕GW at 740 nm, as obtained from Z-scan measurements. Quantum chemical calculations based on time-dependent density functional theory support our experimental data.

Singlet fission in rubrene single crystal: direct observation by femtosecond pump-probe spectroscopy.

The excited state dynamics of rubrene in solution and in the single crystal were studied by femtosecond pump-probe spectroscopy under various excitation conditions. Singlet fission was demonstrated to play a predominant role in the excited state relaxation of the rubrene crystal in contrast to rubrene in solution. Upon 500 nm excitation, triplet excitons form on the picosecond time scale via fission from the lowest excited singlet state. Upon 250 nm excitation, fission from upper excited singlet states is observed within 200 fs.

Chromophore/DNA interactions: femto- to nanosecond spectroscopy, NMR structure, and electron transfer theory.

The mechanism of photoinduced hole injection into DNA has been studied using an integrated approach that combines NMR structural analysis, time-resolved spectroscopy, and quantum-chemical calculations. A covalently linked acridinium derivative, the protonated 9-amino-6-chloro-2-methoxyacridine (X+), is replacing a thymine and separated from either guanine (G) or the easier to oxidize 7-deazaguanine (Z) by one adenine.thymine (A.T) base pair. The key features of this donor/acceptor system are the following: (i) In more than 95% of the duplexes, X+ is located in a central, coplanar position between the neighboring A.T base pairs with its long axis in parallel showing minimal twist and tilt angles (<15 degrees). The complementary adenine base is turned out into the extrahelical space. In a minority of less than 5%, X+ is found to be still attached to the duplex. X+ is most probably associated with one of the phosphates, since it is neither intercalated between more remote base pairs nor bound to sugars or grooves. This minority characterized by an excited state lifetime >10 ns gives rise to a small background signal in time-resolved measurements and contributes predominantly to steady-state fluorescence spectra. (ii) Although the intercalation mode of X+ is well defined, the NMR structure reveals that there are two conformations of X+ with respect to the arrangement of its methoxy substituent. In one conformation, the methoxy group is in the plane of the chromophore, while, in the other extraplanar conformation, the methoxy group forms an angle of 70 degrees with the acridinium ring. The fluorescence decay of 5'-ZAX and 5'-GAX tracts can be fitted to a biexponential function with similar amplitudes, reflecting the oxidation dynamics of G and Z, with the slower rate being determined by larger thermal activation energy. The attribution of biexponential electron transfer (ET) dynamics to the bimodal orientation of the methoxy group at the acridinium is supported by quantum-chemical calculations. These predict a larger free energy change for hole transfer in the nonplanar conformation as compared to the planar one, whereas the difference in the electronic couplings is negligible. (iii) Kinetic studies of the directionality of the 1(X+)* induced hole injection reveal similarly fast decay components in both directions of the duplex, that is, in 5'-ZAX and 5'-XAZ, with the amplitude of the fast component being significantly reduced in 5'-XAZ. The NMR structure shows that local structural deviations from B-DNA are much more pronounced in the 3'-5' direction than in the 5'-3' direction. According to quantum-chemical calculations, the directionality of charge injection is not a universal feature of the DNA duplex but depends critically on the rotation angle of the aromatic plane of the acridinium within the pi stack. The arrangement of X+ in 5'-ZAX and 5'-XAZ corresponds to a conformation with weak directionality of the electronic couplings. The increased disorder in the 3'-5'direction favors slow hole transfer components at the expense of the fast ones. (iv) A comparison of the hole transfer in 5'-GAX and 5'-ZAG shows that classical Marcus theory can explain the ratio of the charge shift rates of more than 2 orders of magnitude on the basis of a free energy difference between G and Z of 0.3 eV. Both NMR structures and quantum-chemical calculations justify the appreciable neglect of differences of electronic couplings as well as in the reorganization energy in 5'-GAX and 5'-ZAG. Despite the attractive concept for the behavior of floppy DNA oligonucleotides, in this acridinium/DNA system, there is no evidence for conformational gating, that is, for fluctuations in the electronic couplings that permit the ET to occur.

Single photon triggered dianion formation in TCNQ and F4TCNQ crystals.

Excited state dynamics in two strong organic electron acceptor systems, TCNQ and F4TCNQ single crystals, was studied. After absorption of a single photon, dianions are formed in both crystals on ultrashort timescale: TCNQ τ < 50 fs, F4TCNQ τ = 4 ps. By use of transient absorption spectroscopy, we demonstrate that the dianion formation in F4TCNQ is mediated by the radical anion precursor which is described by a two-step model. Our measurements show the phenomenon that in this quinoid acceptor crystals in the absence of additional donor molecule, it is possible to resolve the two step formation of a doubly charged anion upon absorption of a single low energy photon (2.6 eV).

On the Mechanism of Long-Range Electron Transfer through DNA.

Hopping between bases of similar redox potentials is the mechanism by which charge transport occurs through DNA. This was shown by rate measurements performed with double strands 1-3. This mechanism explains why hole transfer displays a strong sequence dependence, and postulates that electron transfer in unperturbed DNA should not be dependent on the sequence.

Computed and Experimental Absorption Spectra of the Perovskite CH3NH3PbI3.

Electronic structure and light absorption properties of the perovskite CH3NH3PbI3 are investigated by relativistic density functional theory with quasiparticle GW corrections and many-body interactions. The nature of the Wannier exciton is studied by solving the Bethe-Salpeter equation augmented with the analysis of a conceptual hydrogen-like model. The computed absorption spectrum unravels a remarkable absorption "gap" between the first two absorption peaks. This discontinuity is maintained in the calculated tetragonal structure that, however, is not stable at low temperature. Most importantly, the discontinuity is also observed in the experimental absorption spectrum of the orthorhombic single crystal at low temperature (4 K). However, in contrast to the single crystal, in a polycrystalline perovskite film at 5 K the "gap" is filled by a monotonously increasing absorption throughout the visible range. This feature of thin films points to the potential significance of defect absorption for the excellent light harvesting properties of perovskite-based solar cells.

Distance-dependent activation energies for hole injection from protonated 9-amino-6-chloro-2-methoxyacridine into duplex DNA.

The recent investigation of the apparently anomalous attenuation factor (beta > 1.5 A(-1)) for photoinduced hole injection into DNA duplexes modified by protonated 9-amino-6-chloro-2-methoxyacridine (X+) led to the conclusion that in addition to the electronic couplings, the activation energy must also be distance-dependent. In this communication we report the verification of this postulate by direct measurements of the activation energies for a series of (X+)-modified DNA duplexes which sample an appreciable range of donor-acceptor distances (approximately 4-11 A). The resulting changes in thermal activation energy can be explained within the framework of a distance-dependent reorganization energy.

Picosecond time-resolved fluorescence from blue-emitting chromophore variants Y66F and Y66H of the green fluorescent protein.

The origin of the low steady-state fluorescence quantum yield of some blue-emitting variants of the green fluorescent protein (GFP) is investigated in single-site mutants in which the tyrosine residue at position 66 has been replaced by phenylalanine or by histidine. Time-resolved fluorescence measurements reveal excited-state lifetimes of 74 ps (Y66F) and 0.9 ns (Y66H) at room temperature that increase to values close to the radiative limit as the temperature is lowered. These short lifetimes are explained by temperature-dependent internal conversion. The pronounced difference between the room-temperature lifetimes of the two mutants suggests that hydrogen bonding of the distal aromatic ring plays a more important role than tight packing in the fixation of the chromophore.