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Modeling of charge transfer reactions by EOM methodsElectron transfer reactions are common in biological and synthetic polymers. The rates of these processes can be related to the coupling between the diabatic electronic states that correspond to reactant and product states. Calculations on these systems are difficult due to the propensity of Hartree-Fock solutions to overlocalize charge and break symmetry. |
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Positively charged ethylene dimer is an often-studied prototype system for perpendicular hole conductance. The reaction coordinate slowly interpolates between neutral and cationic geometries of monomers in the dimer.   Electron hopping in ethylene dimer The EOM-CCSD method relies on the unstable Hartree-Fock solution for the open-shell doublet system, which is the positively charged dimer. It predicts excessive charge localization and a cusp on the potential energy surface. In contrast, EOM-IP-CCSD predicts a smooth charge flow along the reaction coordinate as well as smooth PESs. This method employs stable reference wave function of the neutral, which is a closed-shell singlet system, and describes both charge-transfer states in a balanced fashion.  Electron hopping in ethylene dimer by EOM methods Current research includes benchmarking of the EOM-IP-CCSD method and applications to other systems of interest (benzene dimer). Related Publications58. 57. 54. |