Phenothiazine–BODIPY–Fullerene Triads as Photosynthetic Reaction Center Models: Substitution and Solvent Polarity Effects on Photoinduced Charge Separation and Recombination

Novel photosynthetic reaction center model compounds of the type donor₂–donor₁–acceptor, composed of phenothiazine, BF₂‐chelated dipyrromethene (BODIPY), and fullerene, respectively, have been newly synthesized using multistep synthetic methods. X‐ray structures of three of the phenothiazine‐BODIPY intermediate compounds have been solved to visualize the substitution effect caused by the phenothiazine on the BODIPY macrocycle. Optical absorption and emission, computational, and differential pulse voltammetry studies were systematically performed to establish the molecular integrity of the triads. The N‐substituted phenothiazine was found to be easier to oxidize by 60 mV compared to the C‐substituted analogue. The geometry and electronic structures were obtained by B3LYP/6‐31G(dp) calculations (for H, B, N, and O) and B3LYP/6‐31G(df) calculations (for S) in vacuum, followed by a single‐point calculation in benzonitrile utilizing the polarizable continuum model (PCM). The HOMO?1, HOMO, and LUMO were, respectively, on the BODIPY, phenothiazine and fullerene entities, which agreed well with the site of electron transfer determined from electrochemical studies. The energy‐level diagram deduced from these data helped in elucidating the mechanistic details of the photochemical events. Excitation of BODIPY resulted in ultrafast electron transfer to produce PTZ–BODIPY^.+–C₆₀^.?; subsequent hole shift resulted in PTZ^.+–BODIPY–C₆₀^.? charge‐separated species. The return of the charge‐separated species was found to be solvent dependent. In nonpolar solvents the PTZ^.+–BODIPY–C₆₀^.? species populated the ³C₆₀* prior to returning to the ground state, while in polar solvent no such process was observed due to relative positioning of the energy levels. The ¹BODIPY* generated radical ion‐pair in these triads persisted for few nanoseconds due to electron transfer/hole‐shift mechanism.     

Book Review:The Kinetic Theory of Gases: An Anthology of Classic Papers with Historical Commentary. S. G. Brush,World Scientific Publishing Co., River Edge,NJ, 2003

Journal of Statistical Physics -     

Transport in two dimensions. III self-diffusion coefficient at low densities

The low density form of the generalized frequency (s) and wavevector (k) dependent self-diffusion coefficient D(k, s) is calculated, from which the low density forms of related quantities, e.g. the velocity autocorrelation function, are derived. Agreement is obtained with the low density kinetic theory results. A closed form expression for D(k, s) valid over a wide range of densities and times is also given, showing consistency between the asymptotic long time results, obtained previously, and the low density kinetic theory results.     

Magnetism and candidate muon-probe sites in RBa2Cu3O y

Key results of zero-field (ZF) and transverse-field (TF) muon-spin-relaxation (μSR) experiments on superconducting and insulating RBa₂Cu₃O _y (R123 _y , with R=Eu, Gd, Pr and Pr/Y:y=6, 7) are examined. The chemical behavior of the positive muon probe is addressed, and muon-oxygen bonding is shown to occur in all these cuprates. To explain magnetic fields at muon-probe sites in Pr _x Y_1−x Ba₂Cu₃O _y (0<=x<0.5,y=7 andx=0,y=6) samples, improvements on the reported magnetic structures from neutron diffraction are necessary. Cu magnetism in Pr123y (y=6,7) is observed belowT _N1, which is near RT. The magnetism seen belowT _N2 can be interpreted assuming an additional ordering in the Cutt-O chain layers. Alternatively, Pr ordering is also considered as the cause of the second phase transition. Considering the specific muon-probe location, a more detailed interpretation can be provided for the μSR parameters, measured in the normal and mixed states of these unconventional superconductors.     

Nonlinear response theory for inhomogeneous systems in various ensembles

Nonlinear equations governing the relaxation of some macroscopic quantities, a(r,t) are derived using Kubo's response theory, in isolated inhomogeneous systems. The resulting equations contain microcanonical time correlation functions. It is shown how to express these in terms of arbitrary ensemble correlation functions and correction arising from their infinite time behaviour are discussed. In addition it is shown that the concept of local equilibrium must be modified somewhat.