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Theoretical Investigation Of The Ground And Excited States Of Coumarin 151 And Coumarin 120, Robert J. Cave, Kieron Burke, Edward W. Castner Jr.
Theoretical Investigation Of The Ground And Excited States Of Coumarin 151 And Coumarin 120, Robert J. Cave, Kieron Burke, Edward W. Castner Jr.
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We present calculations of various properties of the ground and excited states of Coumarins 151 and 120. These and related coumarins are important in investigating ultrafast solvation processes in liquids and complex solutions as well as being important acceptors in model electron-transfer systems. We calculate the following: (1) the electronic excitation energies to several low-lying singlet states, (2) ground and excited-state dipole moments, (3) solvation effects on excitation energies, and (4) the properties of single Coumarin 151-water complexes. We test our Time-Dependent Density Functional Theory (TDDFT) calculations against CASSCF, CASPT2 (both single and multistate versions), CIS, and ZINDO. Using TDDFT, …
Multistate Effects In Calculations Of The Electronic Coupling Element For Electron Transfer Using The Generalized Mulliken−Hush Method, Michael Rust '01, Jason Lappe '00, Robert J. Cave
Multistate Effects In Calculations Of The Electronic Coupling Element For Electron Transfer Using The Generalized Mulliken−Hush Method, Michael Rust '01, Jason Lappe '00, Robert J. Cave
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A simple diagnostic is developed for the purpose of determining when a third state must be considered to calculate the electronic coupling element for a given pair of diabatic states within the context of the generalized Mulliken−Hush approach (Chem. Phys. Lett. 1996, 275, 15−19). The diagnostic is formulated on the basis of Löwdin partitioning theory. In addition, an effective 2-state GMH expression is derived for the coupling as it is modified by the presence of the third state. Results are presented for (i) a model system involving charge transfer from ethylene to methaniminium cation, (ii) a …
Article Are Hydrogen Bonds Unique Among Weak Interactions In Their Ability To Mediate Electronic Coupling?, Emily Cukier '03, Sarah Daniels '02, Eric Vinson '01, Robert J. Cave
Article Are Hydrogen Bonds Unique Among Weak Interactions In Their Ability To Mediate Electronic Coupling?, Emily Cukier '03, Sarah Daniels '02, Eric Vinson '01, Robert J. Cave
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Superexchange effects on the electronic coupling element for electron transfer are investigated using water dimers and atomic donors and acceptors. We compare the electronic coupling elements obtained with H-bonded dimers to those obtained for other water dimer geometries at given donor−acceptor and oxygen−oxygen distances. The H-bonded orientation does not yield significantly different coupling elements from non-H-bonded orientations at a given oxygen−oxygen distance. In addition, the distance dependence of the coupling mediated by H-bonds is not significantly different from that for other dimer geometries. It is found that protonation of the intervening waters has a significant effect on coupling elements for …
Time-Dependent Density Functional Theory Investigation Of The Ground And Excited States Of Coumarins 102, 152, 153, And 343, Robert J. Cave, Edward W. Castner Jr.
Time-Dependent Density Functional Theory Investigation Of The Ground And Excited States Of Coumarins 102, 152, 153, And 343, Robert J. Cave, Edward W. Castner Jr.
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We present calculations of various properties of the ground and excited electronic states of coumarins 102, 152, 153, and 343. Using density functional theory (DFT) and time-dependent density functional theory (TDDFT), we examine the excitation energies to the S1 and S2 states, the ground and excited-state dipole moments, and the lowest ionization potentials of these coumarins. In the case of C153, we locate two distinct S0 minima due to differing conformations of the julolidyl ring structure and compare properties for the syn and anti conformers. For C343, we examine the possibility of proton transfers in the ground …