997 resultados para State assignment


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The standard highway assignment model in the Florida Standard Urban Transportation Modeling Structure (FSUTMS) is based on the equilibrium traffic assignment method. This method involves running several iterations of all-or-nothing capacity-restraint assignment with an adjustment of travel time to reflect delays encountered in the associated iteration. The iterative link time adjustment process is accomplished through the Bureau of Public Roads (BPR) volume-delay equation. Since FSUTMS' traffic assignment procedure outputs daily volumes, and the input capacities are given in hourly volumes, it is necessary to convert the hourly capacities to their daily equivalents when computing the volume-to-capacity ratios used in the BPR function. The conversion is accomplished by dividing the hourly capacity by a factor called the peak-to-daily ratio, or referred to as CONFAC in FSUTMS. The ratio is computed as the highest hourly volume of a day divided by the corresponding total daily volume. ^ While several studies have indicated that CONFAC is a decreasing function of the level of congestion, a constant value is used for each facility type in the current version of FSUTMS. This ignores the different congestion level associated with each roadway and is believed to be one of the culprits of traffic assignment errors. Traffic counts data from across the state of Florida were used to calibrate CONFACs as a function of a congestion measure using the weighted least squares method. The calibrated functions were then implemented in FSUTMS through a procedure that takes advantage of the iterative nature of FSUTMS' equilibrium assignment method. ^ The assignment results based on constant and variable CONFACs were then compared against the ground counts for three selected networks. It was found that the accuracy from the two assignments was not significantly different, that the hypothesized improvement in assignment results from the variable CONFAC model was not empirically evident. It was recognized that many other factors beyond the scope and control of this study could contribute to this finding. It was recommended that further studies focus on the use of the variable CONFAC model with recalibrated parameters for the BPR function and/or with other forms of volume-delay functions. ^

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We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.