Comparison of CIS- and EOM-CCSD-Calculated Adiabatic Excited-State Structures. Changes in Charge Density on Going to Adiabatic Excited States

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Abstract

The CIS and EOM-CCSD adiabatic geometries for the first excited states of a set of small molecules (C2H4, C2H2, H2CO, H2CS, CS2, CO2, SO2, NO2) have been calculated using the 6-311++G** basis set to see if the former geometries can be good starting points for optimizations at the latter theoretical level. With most of the molecules, there is fairly good agreement between the results from the two methods, and EOM-CCSD gives good agreement with the available experimental data. A detailed discussion of the lowest-lying singlet excited states in CO2 and CS2 is presented, highlighting the pronounced differences in electronic character and equilibrium structure displayed by these isovalent species. The origins of the structural distortions that are frequently found for the adiabatic excited states are examined with the aid of deformation density plots and the electron localization function (ELF).

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