Alberto Acquilino, Gary Scavone
Current State and Future Directions of Technologies for Music Instrument Pedagogy
Frontiers in psychology
many radicalmolecule reactions nonelementary reactions negative activation energies usually proceed two steps exist extensively atmospheric chemistry hydrocarbon fuel combustion extensively studied theoretically experimentally time various models two transition state model steadystate model equilibriumstate model direct elementary dynamics model proposed get kinetic parameters overall reaction paper conversion temperature tc1 defined temperature standard molar gibbs free energy change formation reaction complex equal zero found tc1 direct elementary dynamics model inclusion tunneling correction second step reaction applicable calculate overall reaction rate constants kind reaction system reaction class hydroxyl radical addition alkenes chosen objects study five reactions chosen representative reaction class singlepoint energies calculated using method ccsdtcbs shown highest conversion temperature five reactions 13989 k far usual initial lowtemperature 550 k oxidation chemistry hydrocarbon fuels therefore steadystate approximation method applicable geometry optimizations performed bhhlyp6311gdp level result shows geometric parameters reaction centers conserved hence isodesmic reaction method applicable reaction class validate accuracy scheme comparison electronic energy difference bhhlyp6311gdp level corrected electronic energy difference electronic energy difference ccsdtcbs level performed five representative reactions shown maximum absolute deviation electronic energy difference reduced 254 kcalmol1 correction 058 kcalmol1 correction indicating isodesmic reaction method applicable accurate calculation kinetic parameters largesize molecular systems negative activation energy reaction overall rate constants 44 reactions reaction class hydroxyl radical addition alkenes calculated using transitionstate theory combination isodesmic correction scheme highpressure limit rate rules reaction class developed addition thermodynamic parameter calculated results indicate dynamics model applicable studied reaction class chemical kinetic modeling sensitivity analysis using calculated kinetic data performed combustion ethene results indicate studied reaction important lowtomedium temperature combustion modeling ethene