Spin–Orbit Charge-Transfer Intersystem Crossing (ISC) in Compact Electron Donor–Acceptor Dyads: ISC Mechanism and Application as Novel and Potent Photodynamic Therapy Reagents

Spin–orbit charge-transfer intersystem crossing (SOCT-ISC) is useful for the preparation of heavy atom-free triplet photosensitisers (PSs). Herein, a series of perylene-Bodipy compact electron donor/acceptor dyads showing efficient SOCT-ISC is prepared. The photophysical properties of the dyads were studied with steady-state and time-resolved spectroscopies. Efficient triplet state formation (quantum yield Φ_T=60 %) was observed, with a triplet state lifetime (τ_T=436 μs) much longer than that accessed with the conventional heavy atom effect (τ_T=62 μs). The SOCT-ISC mechanism was unambiguously confirmed by direct excitation of the charge transfer (CT) absorption band by using nanosecond transient absorption spectroscopy and time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The factors affecting the SOCT-ISC efficiency include the geometry, the potential energy surface of the torsion, the spin density for the atoms of the linker, solvent polarity, and the energy matching of the ¹CT/³LE states. Remarkably, these heavy atom-free triplet PSs were demonstrated as a new type of efficient photodynamic therapy (PDT) reagents (phototoxicity, EC₅₀=75 nm ), with a negligible dark toxicity (EC₅₀=78.1 μm ) compared with the conventional heavy atom PSs (dark toxicity, EC₅₀=6.0 μm, light toxicity, EC₅₀=4.0 nm ). This study provides in-depth understanding of the SOCT-ISC, unveils the design principles of triplet PSs based on SOCT-ISC, and underlines their application as a new generation of potent PDT reagents.     

Ranking and unranking planar embeddings

In this paper, we give a formula for computing the number of different planat embeddings of any planar biconnected graph. The enumeration method used in deriving the formula readily gives rise to efficient algorithms for the ranking, unranking and random generation of embeddings of the given graph. We also give linear time algorithms for checking planarity and constructing any particular embedding.     

A flux-vector splitting method for steady Navier-Stokes equations

The flux-vector splitting method is applied to the convective part of the steady Navier-Stokes equations for incompressible flow. By the use of partial upwind differences in the split first-order part and central differences in the second-order part, a set of discrete equations is obtained which can be solved by vector variants of classical relaxation schemes. It is shown that accurate results can be obtained on one of the GAMM backward-facing step test problems.     

Good Lattice Rules in Weighted Korobov Spaces with General Weights

We study the problem of multivariate integration and the construction of good lattice rules in weighted Korobov spaces with general weights. These spaces are not necessarily tensor products of spaces of univariate functions. Sufficient conditions for tractability and strong tractability of multivariate integration in such weighted function spaces are found. These conditions are also necessary if the weights are such that the reproducing kernel of the weighted Korobov space is pointwise non-negative. The existence of a lattice rule which achieves the nearly optimal convergence order is proven. A component-by-component (CBC) algorithm that constructs good lattice rules is presented. The resulting lattice rules achieve tractability or strong tractability error bounds and achieve nearly optimal convergence order for suitably decaying weights. We also study special weights such as finite-order and order-dependent weights. For these special weights, the cost of the CBC algorithm is polynomial. Numerical computations show that the lattice rules constructed by the CBC algorithm give much smaller worst-case errors than the mean worst-case errors over all quasi-Monte Carlo rules or over all lattice rules, and generally smaller worst-case errors than the best Korobov lattice rules in dimensions up to hundreds. Numerical results are provided to illustrate the efficiency of CBC lattice rules and Korobov lattice rules (with suitably chosen weights), in particular for high-dimensional finance problems.     

Time resolved molecular spectroscopy using high power solid state lasers in pulse transmission mode. A re-examination of the Sn← S1 spectra of naphthalene and anthracene

A nanosecond laser spectrometer consisting of a 3nsec ruby/Nd PTM laser, fast detection system and high brightness analysing source is described. An analysis of the geometry considerations is given for crossed beam and collinear arrangement. The excited-state absorption spectra of naphthalene in 3MP at 85°K and 293°K from 14000 to 30000 cm^?1 are given. The results provide a direct method to evaluate the quantum yields for fluorescence φ_f and intersystem crossing φ_T. Also the excited-state absorption spectra of anthracene in PMM from 16000 to 26000 cm^?1 and in 3MP from 26000 to 36000 cm^?1 are reported.     

Two-photon spectroscopy of dipole-forbidden transitions

We have investigated the applicability of CNDO/S-type methods for the calculation of optical spectra of molecules with the special implication that the calculations should not only describe the intense, dipole-allowed transitions which dominate the one-photon absorption spectrum but also those transitions which are one-photon forbidden in first-order approximation. We show that such a method is well suited to predict dipole allowed and dipole forbidden transitions at a similar level of accuracy if double excited configurations are taken into account. In spite of the lack of perfect pairing in NDO methods there are still two types of states which exhibit a different sensitivity towards correlation effects. Therefore, the approximation by which we describe the R-dependence of the Coulomb repulsion gains much more importance than in cases where mainly dipole allowed transitions are of interest. These findings confirm results obtained earlier from theories for which the pairing theorem is valid. The calculated data show an excellent stability with respect to further increase of the number of configurations if at least about 200 energy selected configurations are taken into account.