Theory of anharmonically modified Coriolis coupling in the S1 state of benzene and relation to experiment

Avoided crossings between quasidegenerate rovibrational states in the Doppler-free two-photon excitation of the 141 mode in the S1 excited state of benzene are treated theoretically. Two sets of avoided crossings in plots of spectral line frequency vs J at a given K and DeltaK have been reported experimentally between an initially prepared "light" state (141 in zeroth order) and dark states, namely, one which in zeroth order is a 51101161 state, the other being in zeroth order a 62111 and/or possibly a 31161 state, implicated earlier by Neusser et al. The identification of these states makes the phenomenon an excellent candidate for treatment of the avoided crossing via a Van Vleck transformation, no other basis set states being needed for the diagonalization in order to extract the important features. Two successive transformations are used for handling direct coupling and coupling via virtual states. The dominant calculated contribution to the coupling is, jointly, Coriolis plus cubic–cubic anharmonic interactions between vibrational modes.Playing less of a role are Coriolis terms in which the inverse moment of inertia tensor is expanded up to quadratic terms in the coordinates. There results a 5×5 (for coupling to 51101161 ) and a 3×3 (for coupling to 62111 or 31161 ) matrix of the transformed Hamiltonian, each of which can also be described, if desired, to a very good approximation by a 2×2 matrix. The coupling element V0 and the difference of the rotational constants for the light and dark states (DeltaB) are obtained from the plots of line position vs J(J+1) obtained. For the 141 to 51101161 and for the 141 to 62111 couplings the theoretical results are in reasonable agreement with the experimental results, no adjustable parameters being employed. For a coupling of 141 to 31161 the calculated V0 would be much too high compared with experiment (a factor of 10), the coupling involving the exchange of only three instead of four vibrational quanta. A situation in which the 141 state is coupled to the 62111 state to yield an avoided crossing and off-resonantly coupled to the 31161 state would be consistent with some experimental results and not affect the reasonable agreement of the slope difference and splitting for the avoided crossing plots

Theory of fluorescence excitation spectra using anharmonic-coriolis coupling in S1 and internal conversion to S0. I. General formalism

A treatment of one- or two-photon fluorescence excitation spectra is described using the vibration–rotation coupling of zeroth order states in the excited electronic state and nonadiabatic coupling to the ground state. Using perturbation theory, experimental harmonic frequencies, an anharmonic force field, and various theoretical Coriolis coupling constants, a quasistationary molecular eigenstate in an excited electronic state S1 is first calculated. The S1 eigenstate is then coupled via the nonadiabatic nuclear kinetic energy operator (internal conversion) to rovibronic states in the ground state manifold, the latter states approximated in a simple manner. A search algorithm is used to select the S1 dark states and the S0 states. Both the perturbation theory coefficient and the Franck–Condon factors are employed in the evaluation function used in the search. The results are applied in part II to the channel three problem in benzene

A Call for Proactive Human–Bear Conflict Mitigation

This commentary serves as a call to action for the creation of proactive mitigation efforts to lessen human–bear conflict based on comprehensive predictive data models

Exploring Students\u27 Perceptions of Academically Based Living-Learning Communities

This qualitative study employed focus group interviews to explore students\u27 perceptions of three well established academically based living-learning communities at a large, land-grant university in the Midwest. Three themes emerged that illustrated students\u27 perceptions of a culture that promoted seamless learning, a scholarly environment, and an ethos of relatedness among faculty, staff, and peers. Implications for practice and future research are discussed

Probabilistic forecasting of heterogeneous consumer transaction-sales time series

We present new Bayesian methodology for consumer sales forecasting. With a focus on multi-step ahead forecasting of daily sales of many supermarket items, we adapt dynamic count mixture models to forecast individual customer transactions, and introduce novel dynamic binary cascade models for predicting counts of items per transaction. These transactions-sales models can incorporate time-varying trend, seasonal, price, promotion, random effects and other outlet-specific predictors for individual items. Sequential Bayesian analysis involves fast, parallel filtering on sets of decoupled items and is adaptable across items that may exhibit widely varying characteristics. A multi-scale approach enables information sharing across items with related patterns over time to improve prediction while maintaining scalability to many items. A motivating case study in many-item, multi-period, multi-step ahead supermarket sales forecasting provides examples that demonstrate improved forecast accuracy in multiple metrics, and illustrates the benefits of full probabilistic models for forecast accuracy evaluation and comparison. Keywords: Bayesian forecasting; decouple/recouple; dynamic binary cascade; forecast calibration; intermittent demand; multi-scale forecasting; predicting rare events; sales per transaction; supermarket sales forecastingComment: 23 pages, 5 figures, 1 tabl

A Randomized Parallel Sorting Algorithm With an Experimental Study

Previous schemes for sorting on general-purpose parallel machines have had to choose between poor load balancing and irregular communication or multiple rounds of all-to-all personalized communication. In this paper, we introduce a novel variation on sample sort which uses only two rounds of regular all-to-all personalized communication in a scheme that yields very good load balancing with virtually no overhead. Moreover, unlike previous variations, our algorithm efficiently handles the presence of duplicate values without the overhead of tagging each element with a unique identifier. This algorithm was implemented in Split-C and run on a variety of platforms, including the Thinking Machines CM-5, the IBM SP-2, and the Cray Research T3D. We ran our code using widely different benchmarks to examine the dependence of our algorithm on the input distribution. Our experimental results illustrate the efficiency and scalability of our algorithm across different platforms. In fact, it seems to..

Announcement of a special virtual issue on the EuroGRAPHENE program

The Carbon journal is pleased to announce the publication of a virtual special issue on research funded by the EuroGRAPHENE program of the European Science Foundation. In order to ensure rapid publication, the contributed primary research articles have already appeared in regular Carbon volumes over the course of 2014, and are now compiled together as a virtual special issue on the journal website.1 The present article by our team of guest editors serves as an introduction to this special issue, and also a commentary on the graphene field and the important role played by the EuroGRAPHENE program

Comparación de algoritmos multiobjetivo inspirados en búsqueda armónica, búsqueda cuco y murciélagos para la ubicación de generación distribuida renovable

Electric power losses have a significant impact on the total costs of distribution networks. The use of renewable energy sources is a major alternative to improve power losses and costs, although other important issues are also enhanced such as voltage magnitudes and network congestion. However, determining the best location and size of renewable energy generators can be sometimes a challenging task due to a large number of possible combinations in the search space. Furthermore, the multiobjective functions increase the complexity of the problem and metaheuristics are preferred to find solutions in a relatively short time. This paper evaluates the performance of the cuckoo search (CS), harmony search (HS), and bat-inspired (BA) algorithms for the location and size of renewable distributed generation (RDG) in radial distribution networks using a multiobjective function defined as minimizing the energy losses and the RDG costs. The metaheuristic algorithms were programmed in Matlab and tested using the 33-node radial distribution network. The three algorithms obtained similar results for the two objectives evaluated, finding points close to the best solutions in the Pareto front. Comparisons showed that the CS obtained the minimum results for most points evaluated, but the BA and the HS were close to the best solution.Las pérdidas eléctricas tienen un impacto significativo en los costos totales de las redes de distribución. El uso de las energías renovables es una gran alternativa para mejorar las pérdidas y los costos, aunque también otros problemas en las magnitudes de las tensiones y la congestión de la red pueden ser mejorados. Sin embargo, determinar la mejor localización y dimensionamiento de generadores eléctricos renovables puede ser a veces una tarea difícil debido al gran número de combinaciones posibles existentes en el espacio de búsqueda. Además, el uso de funciones multiobjetivo incrementa la complejidad del problema y se prefiere usar las metaheurísticas para encontrar soluciones en un tiempo relativamente corto. En este trabajo se evalúa el desempeño de los algoritmos inspirados en búsqueda cuco, búsqueda armónica y murciélagos para la localización y dimensionamiento de la generación distribuida renovable en redes de distribución radiales, usando funciones como la minimización de las pérdidas de energía y los costos de la generación distribuida renovable. Las metaheurísticas fueron programadas en Matlab y evaluadas usando la instancia denominada red de distribución radial de 33 nodos. Los tres algoritmos evaluados obtuvieron resultados similares para los dos objetivos evaluados, encontrando Frentes de Pareto cercanos a las mejores soluciones. La comparación realizada mostró que la búsqueda cuco obtiene los mejores resultados, pero los algoritmos inspirados en murciélagos y búsqueda armónica obtuvieron resultados cercanos a la mejor solución

Hole spin polarization in GaAlAs:Mn structures

A self-consistent calculation of the electronic properties of GaAlAs:Mn magnetic semiconductor quantum well structures is performed including the Hartree term and the sp-d exchange interaction with the Mn magnetic moments. The spin polarization density is obtained for several structure configurations. Available experimental results are compared with theory.Comment: 4 page