No abstract

A mechanistic insight into the hetero- and homodimerizations (HETD and HOMD) of styrenes promoted by hypervalent iodine reagents (HVIRs; DMP and PIDA) and facilitated by HFIP to yield all trans cyclobutanes is reported using density functional theory (DFT) calculations. The HFIP molecules lower the energy of the single electron oxidation (SEO) or initiation as a result of strong hydrogen bonding interactions that substantially stabilize the frontier orbitals before and after electron addition. The HETD or HOMD is a radically-characterized π-π stacked head-to-head stepwise [2+2] cycloaddition initiated via SEO by DMP or PIDA, respectively. DFT results supported by quasiclassical molecular dynamics simulations show that HOMD is a competing pathway to HETD although the latter is relatively faster, in accordance with experimental observations. The initiation is a rate-determining step as a thermodynamically endergonic and propagation is accomplished by radically-cationic hetero- and homodimerized intermediate as propagation is faster than single electron reduction (SER) or termination by radically-anionic HVIRs. Initiation by DMP found to be faster and less endergonic than by PIDA due to (1) the energy gap of electron transfer in a SEO step by I(V) is lower than I(III) and (2) the SOMO energy of the radical anion I(V) is lower than I(III). Furthermore, the presence of p-methoxy group is essential to underpin the SEO by which the more thermodynamically favorable SEO leads to a successful cycloaddition as the thermodynamic term represents a major contribution in the initiative barrier.

Due to the increase in the emission of greenhouse gases, the hydrologic cycle is being altered on the daily basis. This has affected the variations in relations of intensity, duration, and frequency of rainfall events. Intensity Duration Frequency (IDF) curves describe the relationship between rainfall intensity, rainfall duration and return period. IDF curves are one of the most often applied implements in water resource engineering, in areas such as for operating, planning and designing of water resource projects, or for numerous engineering projects aimed at controlling floods. In particular, IDF curves for precipitation answer problems of improper drainage systems or conditions and extreme characters of precipitation which are the main cause of floods in Nyabugogo catchment. This study aims to establish Rainfall IDF empirical equations, curves and hydrological discharge (predicted peak rate of runoff (Qlogy)) equations for eight Districts that will be used for designing an appropriate and sustainable hydraulic structures for controlling flood to reduce potential loss of human and aquatic life, degradation of water, air and soil quality and property damage and economic lessen caused by flood in Nyabugogo catchment. However Goodness of Fit tests revealed that Gumbel’s Extreme-Value Distribution method appears to have the most appropriate fit compared with Pearson type III distribution for validating the Intensity-Duration-Frequency curves and equations through the use of daily annual for each meteorological station. The findings of the study show that the intensity of rainfall increases with a decrease in rainfall duration. Additionally, a rainfall of every known duration will have a higher intensity if its return period is high, while the predicted peak rate of runoff (Qlogy) increases also with an increase in the intensity of rainfall.