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In this paper, we examine decay and fragmentation of core-excited and core-ionized water molecules combining quantum chemical calculations and electron-energy-resolved electron–ion coincidence spectroscopy. The experimental technique allows us to connect electronic decay from core-excited states, electronic transitions between ionic states, and dissociation of the molecular ion. To this end, we calculate the minimum energy dissociation path of the core-excited molecule and the potential energy surfaces of the molecular ion. Our measurements highlight the role of ultra-fast nuclear motion in the 1 a 1 − 1 4 a 1 core-excited molecule in the production of fragment ions. OH+ fragments dominate for spectator Auger decay. Complete atomization after sequential fragmentation is also evident through detection of slow H+ fragments. Additional measurements of the non-resonant Auger decay of the core-ionized molecule (1 a 1 − 1 ) to the lower-energy dication states show that the formation of the OH+ + H+ ion pair dominates, whereas sequential fragmentation OH+ + H+ → O + H+ + H+ is observed for transitions to higher dication states, supporting previous theoretical investigations. [ABSTRACT FROM AUTHOR]

Five neural network (NN) models, a linear statistical model and a deterministic modelling system (DET) were evaluated for the prediction of urban NO2 and PM10 concentrations. The model evaluation work considered the sequential hourly concentration time series of NO2 and PM10, which were measured at two stations in central Helsinki, from 1996 to 1999. The models utilised selected traffic flow and pre-processed meteorological variables as input data. An imputed concentration dataset was also created, in which the missing values were replaced, in order to obtain a harmonised database that is well suited for the inter-comparison of models. Three statistical criteria were adopted: the index of agreement (IA), the squared correlation coefficient (R2) and the fractional bias. The results obtained with various non-linear NN models show a good agreement with the measured concentration data for NO2; for instance, the annual mean of the IA values and their standard deviations range from 0.86±0.02 to 0.91±0.01. In the case of NO2, the non-linear NN models produce a range of model performance values that are slightly better than those by the DET. NN models generally perform better than the statistical linear model, for predicting both NO2 and PM10 concentrations. In the case of PM10, the model performance statistics of the NN models were not as good as those for NO2 over the entire range of models considered. However, the currently available NN models are neither applicable for predicting spatial concentration distributions in urban areas, nor for evaluating air pollution abatement scenarios for future years. [Copyright &y& Elsevier]

The solvation of alkali-halides in water clusters at nanoscale is studied by photoelectron spectroscopy using synchrotron radiation. The Na 2p, K 3p, Cl 2p, Br 3d, and I 4d core level binding energies have been measured for salt-containing water clusters. The results have been compared to those of alkali halide clusters and the dilute aqueous salt solutions. It is found that the alkali halides dissolve in small water clusters as ions. [ABSTRACT FROM AUTHOR]

In this paper, we examine decay and fragmentation of core-excited and core-ionized water molecules combining quantum chemical calculations and electron-energy-resolved electron-ion coincidence spectroscopy. The experimental technique allows us to connect electronic decay from core-excited states, electronic transitions between ionic states, and dissociation of the molecular ion. To this end, we calculate the minimum energy dissociation path of the core-excited molecule and the potential energy surfaces of the molecular ion. Our measurements highlight the role of ultra-fast nuclear motion in the 1a 1 -1 4a 1 core-excited molecule in the production of fragment ions. OH + fragments dominate for spectator Auger decay. Complete atomization after sequential fragmentation is also evident through detection of slow H + fragments. Additional measurements of the non-resonant Auger decay of the core-ionized molecule (1a 1 -1 ) to the lower-energy dication states show that the formation of the OH + + H + ion pair dominates, whereas sequential fragmentation OH + + H + → O + H + + H + is observed for transitions to higher dication states, supporting previous theoretical investigations.