Atomic Group Decomposition of Charge Transfer Excitation Global Indexes.

A model for decomposing the Le Bahers, Adamo, and Ciofini Charge Transfer (CT) Excitations global indexes ( J. Chem. Theory Comput. 2011, 7, 2498-2506) into molecular subdomains contributions is presented and a software, DOCTRINE (atomic group Decomposition Of the Charge TRansfer INdExes) for the implementation of this novel model has been coded. Although our method applies to any fuzzy or to any disjoint exhaustive partitioning of the real space, it is here applied using a definition of chemically relevant molecular subdomains based on the Atoms in Molecules Bader basins. This choice has the relevant advantage of associating intra or inter subdomain contributions to rigorously defined quantum objects, yet bearing a clear chemical meaning. Our method allows for a quantitative evaluation of the subdomain contributions to the charge transfer, the charge transfer excitation length and the dipole moment change upon excitation. All these global indexes may be obtained either from the electron density increment or the electron density depletion upon excitation. However, the subdomain contributions obtained from the two distributions generally differ, therefore allowing to distinguish whether the contribution to a given property of a given subdomain is dominated by one of the two distributions or if both are playing a significant role. As a toy system for the first application of our model, a typical [D-π-A, π = conjugated bridge] compound belonging to the merocyanine dyes family is selected, and the first four excited states of this compound in a strongly polar protic solvent and in a weakly polar solvent are thoroughly investigated.