Measurement of the B-->pi l nu branching fraction and determination of absolute value of V(ub) with tagged B mesons

We report a measurement of the B-->pi l nu branching fraction based on 211 fb(-1) of data collected with the BABAR detector. We use samples of B0 and B+ mesons tagged by a second B meson reconstructed in a semileptonic or hadronic decay and combine the results assuming isospin symmetry to obtain B(B(0)-->pi- l+ nu) = (1.33+/-0.17stat+/-0.11syst) x 10(-4). We determine the magnitude of the Cabibbo-Kobayashi-Maskawa matrix element absolute value V(ub) by combining the partial branching fractions measured in ranges of the momentum transfer squared and theoretical calculations of the form factor. Using a recent lattice QCD calculation, we find absolute value V(ub) = (4.5+/-0.5stat+/-0.3syst(+0.7) -0.5FF x 10(-3), where the last error is due to the normalization of the form factor.     

Measurement of the branching fraction and photon energy moments of B-->Xs gamma and A(CP)(B --> X(s+d gamma))

The photon spectrum in B-->Xs gamma decay, where Xs is any strange hadronic state, is studied using a data sample of 88.5 x 10(6) e+ e- --> Upsilon(4S) --> BB decays collected by the BABAR experiment at the Stanford Linear Accelerator Center. The partial branching fraction, DeltaB(B --> Xs gamma) = (3.67+/-0.29(stat)+/-0.34(syst)+/-0.29(model)) x 10(-4), the first moment = 2.288+/-0.025+/-0.017+/-0.015 GeV, and the second moment E2(gamma) = 0.0328+/-0.0040+/-0.0023+/-0.0036 GeV2 are measured for the photon energy range 1.9 GeV < E gamma < 2.7 GeV. They are also measured for narrower E gamma ranges. The moments are then fit to recent theoretical calculations to extract the heavy quark expansion parameters m(b) and mu2(pi) and to extrapolate the partial branching fraction to E gamma > 1.6 GeV. In addition, the direct CP asymmetry A(CP)(B-->X(s+d gamma) is measured to be -0.110+/-0.115(stat)+/-0.017(syst).     

Ab initio optical rotatory dispersion and electronic circular dichroism spectra of (S)-2-chloropropionitrile

Coupled-cluster and density-functional methods have been used to determine specific rotations and electronic circular dichroism (ECD) rotational strengths for (S)-2-chloropropionitrile. Coupled-cluster specific rotations using both the length- and velocity-gauge representations of the electric-dipole operator, computed with basis sets of triple-zeta quality containing up to 326 functions, compare very well with recently reported gas-phase cavity-ring-down polarimetry data. ECD rotational strengths for the six lowest-lying excited states are found to vary in sign, and the second excited state, which has a larger rotational strength than the first by a factor of 4, was found to yield a much larger contribution (by a factor of 10) to the overall negative specific rotation observed both experimentally and theoretically. However, both valence and Rydberg states appear to make substantial contributions to the total rotation, often of opposite sign from the converged/linear-response result. Furthermore, the sum-over-states approach was found to be inadequate for reproducing the specific rotations derived from the linear-response approach, even when 100 excited states (well beyond the estimated ionization limit) were included in the summation. Density-functional specific rotations using the B3LYP functional with basis sets of quadruple-zeta quality containing up to 588 functions are found to be too large compared to experiment by approximately a factor of 2. This error appears to be related to both the underestimation of the electronic excitation energies, as well as concomitant overestimation of the corresponding ECD rotational strengths. Although earlier studies reported good agreement between density-functional specific rotations and experiment when electric-field-dependent functions were used in conjunction with a double-zeta-quality basis set, the results reported here, which are near the basis-set limit, suggest that this agreement may be fortuitous.     

Observation of the semileptonic decays B-->D*tau-nutau and evidence for B-->Dtau-nutau

We present measurements of the semileptonic decays B--->D0tau-nutau, B--->D*0tau-nutau, B0-->D+tau-nutau, and B0-->D*+tau-nutau, which are potentially sensitive to non-standard model amplitudes. The data sample comprises 232x10(6) Upsilon(4S)-->BB decays collected with the BABAR detector. From a combined fit to B- and B0 channels, we obtain the branching fractions B(B-->Dtau-nutau)=(0.86+/-0.24+/-0.11+/-0.06)% and B(B-->D*tau-nutau)=(1.62+/-0.31+/-0.10+/-0.05)% (normalized for the B0), where the uncertainties are statistical, systematic, and normalization-mode-related.     

Transition Metal Free Cycloamination of Prenyl Carbamates and Ureas Promoted by Aryldiazonium Salts

Upon treatment with aryldiazonium salts, prenyl carbamates and ureas undergo redox‐neutral azocycloamination. In general, N‐aryl O‐prenyl carbamates cyclize in a photocatalytic reaction with visible light and an organic dye. With electron‐deficient diazonium salts, electronic matching with an electron‐rich N‐aryl substituent results in a reaction proceeding in the ground state, without either light or photocatalyst. Cyclic voltammetry suggests that this radical reaction is initiated by hydrogen‐atom abstraction mediated by an aryl radical, followed by a radical addition cascade and proton‐coupled hole propagation. The reaction proceeds at room temperature in short reaction times, and a range of functional groups is tolerated.     

In search of efficient 5-endo-dig cyclization of a carbon-centered radical: 40 years from a prediction to another success for the Baldwin rules

Despite being predicted to be stereoelectronically favorable by the Baldwin rules, efficient formation of a C-C bond through a 5-endo-dig radical cyclization remained unknown for more than 40 years. This work reports a remarkable increase in the efficiency of this process upon beta-Ts substitution, which led to the development of an expedient approach to densely functionalized cyclic 1,3-dienes. Good qualitative agreement between the increased efficiency and stereoselectivity for the 5-endo-dig cyclization of Ts-substituted vinyl radicals and the results of density functional theory analysis further confirms the utility of computational methods in the design of new radical processes. Although reactions of Br atoms generated through photochemical Ts-Br bond homolysis lead to the formation of cyclic dibromide side products, the yields of target bromosulfones in the photochemically induced reactions can be increased by recycling the dibromide byproduct into the target bromosulfones through a sequence of addition/elimination reactions at the exocyclic double bond. Discovery of a relatively efficient radical 5-endo-dig closure, accompanied by a C-C bond formation, provides further support to stereoelectronic considerations at the heart of the Baldwin rules and fills one of the last remaining gaps in the arsenal of radical cyclizations.     

The Genus of a Digital Image Boundary Is Determined by Its Foreground,Background, and Reeb Graphs

We prove that the genus of the boundary of a digital image is precisely half of the sum of the cycle ranks of three particular graphs: the "foreground graph" and "background graph," which capture topological information about the digital image and its complement, respectively, and the Reeb graph, relative to the natural height function, associated with the digital image's boundary. We prove several additional results, including a characterization of when the cycle rank of the Reeb graph fails to equal the genus of the digital image's boundary (which can happen by virtue of the failure of the natural height function on the boundary of the digital image to be a Morse function).     

The current state of ab initio calculations of optical rotation and electronic circular dichroism spectra

The current ability of ab initio models to compute chiroptical properties such as optical rotatory dispersion and electronic circular dichroism spectra is reviewed. Comparison between coupled cluster linear response theory and experimental data (both gas and liquid phase) yields encouraging results for small to medium-sized chiral molecules including rigid species such as (S)-2-chloropropionitrile and (P)-[4]triangulane, as well as conformationally flexible molecules such as (R)-epichlorohydrin. More problematic comparisons are offered by (S)-methyloxirane, (S)-methylthiirane, and (1S,4S)-norbornenone, for which the comparison between theory and experiment is much poorer. The impact of basis-set incompleteness, electron correlation, zero-point vibration, and temperature are discussed. In addition, future prospects and obstacles for the development of efficient and reliable quantum chemical models of optical activity are discussed, including the problem of gauge invariance, scaling of the coupled cluster approach with system size, and solvation.     

The lowest 2A' excited state of the water-hydroxyl complex

Vertical and adiabatic excitation energies of the lowest (2)A(') excited state in the water-hydroxyl complex have been determined using coupled cluster, multireference configuration interaction, multireference perturbation theory, and density-functional methods. A significant redshift of about 0.4 eV in the vertical excitation energy of the complex compared to that of the hydroxyl radical monomer is found with the coupled cluster calculations validating previous results. Electronic excitation leads to a structure with near-equal sharing of the hydroxyl hydrogen by both oxygen atoms and a concomitantly large redshift of the adiabatic excitation energy of approximately 1 eV relative to the vertical excitation energy. The combination of redshifts ensures that the electronic transition in the complex lies well outside the equivalent excitation in the hydroxyl radical monomer. The complex is approximately five times more strongly bound in the excited state than in the ground state.