Efficient light harvesting by sequential energy transfer across aggregates in polymers of finite conjugational segments with short aliphatic linkages.

Interactions between lumophores have a critical influence on the photophysical properties of conjugated polymers. We synthesized a new series of light-harvesting polymers (poly-DSBs, I-IV) of dialkyloxy- or dialkyl-substituted distyrylbenzene (the substituents being methoxy, 2-ethylhexyloxy, and cyclohexyl) with short aliphatic linkage (methylene or ethylene) and examined the effects of interactions between lumophores and of chemical structures on the absorption, emission, and excitation spectra. The proximity between distyrylbenzene lumophores was shown to be critical to the interactions between lumophores and to the energy-transfer processes. In concentrated solutions and solid films, intermolecular aggregates exist resulting from different extents of interactions between lumophores and are found to involve at least three species: loose, compact, and the most aligned aggregates as observed by photoluminescence and excitation spectroscopies. We also found, for the first time, sequential energy transfer from individual lumophores to the most compact, aligned aggregates via the looser intermolecular aggregates, as observed directly by time-resolved fluorescence spectroscopy. Such a process mimics energy transfer in photosynthesis units and is so efficient such that the fluorescence color can be red-shifted drastically by the presence of comparatively few aggregates and that the light evolved from concentrated solutions and films of poly-DSBs I-IV is entirely or almost the aggregation emission. Although the sequential energy-transfer process in fully conjugated electro-/photoluminescent polymers due to inhomogenity other than distributed conjugation lengths has never been directly observed at room temperature, we suggest that events similar to those observed in poly-DSBs in conjugated polymers could occur but on a much shorter time scale, i.e., a few picoseconds.     

Intrachain chromophore interactions in silanylene‐spaced divinylbenzene copolymers

A range of silanylene‐spaced divinylbenzene copolymers ( 1 ) and the corresponding monomers ( 2 ) have been synthesized by the rhodium‐catalyzed hydrosilylation of the corresponding bisalkynes with bissilyl hydrides, and the photophysical properties of 1 and 2 have been investigated. The silicon moiety in 1 serves as an insulating tetrahedral spacer that makes 1 highly folded. The two chromophores may be in close proximity such that a ground‐state intrachain interaction between two conjugated moieties through space might occur. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2218–2231, 2003     

Thorpe-Ingold effect on the conformation and photophysical properties of dialkylsilylene-spaced divinylarene copolymers

Geminal disubstitution on silicon in dialkylsilylene-spaced divinylarene copolymers may dictate the conformation and photophysical properties of the copolymers, bulky (i)Pr substituted copolymers being more folded than Me substituent analogues.     

Fast transform from an adaptive multi-wavelet representation to a partial Fourier representation

We present a fast algorithm to compute the partial transformation of a function represented in an adaptive pseudo-spectral multi-wavelet representation to a partial Fourier representation. Such fast transformations are useful in many contexts in physics and engineering, where changes of representation from a piece wise polynomial basis to a Fourier basis. The algorithm is demonstrated for a Gaussian in one and in three dimensions. For 2D, we apply this approach to a Gaussian in a periodic domain. The accuracy and the performance of this method is compared with direct summation.     

Adaptive discontinuous Galerkin methods in multiwavelets bases

We use a multiwavelet basis with the Discontinuous Galerkin (DG) method to produce a multi-scale DG method. We apply this Multiwavelet DG method to convection and convection-diffusion problems in multiple dimensions. Merging the DG method with multiwavelets allows the adaptivity in the DG method to be resolved through manipulation of multiwavelet coefficients rather than grid manipulation. Additionally, the Multiwavelet DG method is tested on non-linear equations in one dimension and on the cubed sphere.     

Multiresolution quantum chemistry: basic theory and initial applications

We describe a multiresolution solver for the all-electron local density approximation Kohn-Sham equations for general polyatomic molecules. The resulting solutions are obtained to a user-specified precision and the computational cost of applying all operators scales linearly with the number of parameters. The construction and use of separated forms for operators (here, the Green's functions for the Poisson and bound-state Helmholtz equations) enable practical computation in three and higher dimensions. Initial applications include the alkali-earth atoms down to strontium and the water and benzene molecules.     

Combining Light Harvesting and Electron Transfer in Silica–Titania‐Based Organic–Inorganic Hybrid Materials

A convenient protocol to fabricate an organic–inorganic hybrid system with covalently bound light‐harvesting chromophores (stilbene and terphenylene–divinylene) and an electron acceptor (titanium oxide) is described. Efficient energy‐ and electron‐transfer processes may take place in these systems. Covalent bonding between the acceptor chromophores and the titania/silica matrix would be important for electron transfer, whereas fluorescence resonant energy transfer (FRET) would strongly depend on the ratio of donor to acceptor chromophores. Time‐resolved spectroscopy was employed to elucidate the detailed photophysical processes. The coupling of FRET and electron transfer was shown to work coherently to lead to photocurrent enhancement. The photocurrent responses reached a maximum when the hybrid‐material thin film contained 60 % acceptor and 40 % donor.     

The absorption and emission spectra of 1,4-di(2-phenylvinyl)benzene. A theoretical analysis

The ground and excited states of 1,4-di (2-phenylvinyl)benzene (PPV3) were studied theoretically and compared with experimental results. The equilibrium geometries of the ground states were found to be nonplanar despite the π conjugation in PPV3; however, the equilibrium geometry of the first excited state of PPV3 is planar, due to the increased π character between the benzene and ethylene units. The electronic structures of the excited state were investigated using the INDO/S-CIS method. The lack of a mirror-image relationship between the absorption and fluorescence spectra of PPV3, obtained experimentally, was analyzed theoretically. It was demonstrated that structural inhomogeneity might be the reason for the particular spectral band shape. Received: 12 April 1999 / Accepted: 15 June 1999 / Published online: 4 October 1999     

Toward high-performance computational chemistry: II. A scalable self-consistent field program

We discuss issues in developing scalable parallel algorithms and focus on the distribution, as opposed to the replication, of key data structures. Replication of large data structures limits the maximum calculation size by imposing a low ratio of processors to memory. Only applications which distribute both data and computation across processors are truly scalable. The use of shared data structures that may be independently accessed by each process even in a distributed memory environment greatly simplifies development and provides a significant performance enhancement. We describe tools we have developed to support this programming paradigm. These tools are used to develop a highly efficient and scalable algorithm to perform self-consistent field calculations on molecular systems. A simple and classical strip-mining algorithm suffices to achieve an efficient and scalable Fock matrix construction in which all matrices are fully distributed. By strip mining over atoms, we also exploit all available sparsity and pave the way to adopting more sophisticated methods for summation of the Coulomb and exchange interactions. © 1996 by John Wiley & Sons, Inc.     

Two-photon excited fluorescence of nitrogen-vacancy centers in proton-irradiated type Ib diamond

Two-photon fluorescence spectroscopy of negatively charged nitrogen-vacancy [(N-V)-] centers in type Ib diamond single crystals have been studied with a picosecond (7.5 ps) mode-locked Nd:YVO(4) laser operating at 1064 nm. The (N-V)- centers were produced by radiation damage of diamond using a 3 MeV proton beam, followed by thermal annealing at 800 degrees C. Prior to the irradiation treatment, infrared spectroscopy of the C-N vibrational modes at 1344 cm(-1) suggested a nitrogen content of 109 +/- 10 ppm. Irradiation and annealing of the specimen led to the emergence of a new absorption band peaking at approximately 560 nm. From a measurement of the integrated absorption intensity of the sharp zero-phonon line (637 nm) at liquid nitrogen temperature, we determined a (N-V)- density of (4.5 +/- 1.1) x 10(18) centers/cm3 (or 25 +/- 6 ppm) for the substrate irradiated at a dose of 1 x 1016) H(+)/cm(2). Such a high defect density allowed us to observe two-photon excited fluorescence and measure the corresponding fluorescence decay time. No significant difference in the spectral feature and fluorescence lifetime was observed between one-photon and two-photon excitations. Assuming that the fluorescence quantum yields are the same for both processes, a two-photon absorption cross section of sigma(TPA) = (0.45 +/- 0.23) x 10(-50) cm(4).s/photon at 1064 nm was determined for the (N-V)- center based on its one-photon absorption cross section of sigma(OPA) = (3.1 +/- 0.8) x 10(-17) cm2 at 532 nm. The material is highly photostable and shows no sign of photobleaching even under continuous two-photon excitation at a peak power density of 3 GW/cm(2) for 5 min.