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Full-Text Articles in Physical Sciences and Mathematics
Solvent As Electron Donor: Donor/Acceptor Electronic Coupling Is A Dynamical Variable, Edward W. Castner Jr., Darcy Kennedy '00, Robert J. Cave
Solvent As Electron Donor: Donor/Acceptor Electronic Coupling Is A Dynamical Variable, Edward W. Castner Jr., Darcy Kennedy '00, Robert J. Cave
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We combine analysis of measurements by femtosecond optical spectroscopy, computer simulations, and the generalized Mulliken−Hush (GMH) theory in the study of electron-transfer reactions and electron donor−acceptor interactions. Our focus is on ultrafast photoinduced electron-transfer reactions from aromatic amine solvent donors to excited-state acceptors. The experimental results from femtosecond dynamical measurements fall into three categories: six coumarin acceptors reductively quenched by N,N-dimethylaniline (DMA), eight electron-donating amine solvents reductively quenching coumarin 152 (7-(dimethylamino)-4-(trifluoromethyl)coumarin), and reductive quenching dynamics of two coumarins by DMA as a function of dilution in the nonreactive solvents toluene and chlorobenzene. Applying a combination of molecular …
On The Vertical And Adiabatic Excitation Energies Of The 21a(G), State Of Trans-1,3-Butadiene, Jason Lappe '00, Robert J. Cave
On The Vertical And Adiabatic Excitation Energies Of The 21a(G), State Of Trans-1,3-Butadiene, Jason Lappe '00, Robert J. Cave
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The excitation energy to the 21Ag state of trans-1,3-butadiene is examined using a variety of ab initio electronic structure techniques. While analogous states have been shown to be the lowest singlet excited states for all longer polyenes, for butadiene the position of the 21Ag state relative to the HOMO → LUMO excitation (11Bu) has been difficult to establish theoretically. We employ a variety of methods (CASSCF, CASPT2, MRSDCI, QDVPT) to examine both the vertical and adiabatic excitation energies for this state. At the ground-state geometry, the vertical excitation energies …