MD–DIM simulations of the 3Πg(ion-pair)→3Πu(valence) red-shifted transitions of Cl2 in neon matrices

Molecular Photodynamics in Rare Gas Solids

“…115 Two important conclusions can be reiterated from these works: first, in considering the energetics of a system such as a hydrogen halide, even in the "ground" electronic surface, ionic configurations cannot be ignored; second, DIIS can be useful in such treatments by including the mixing between ionic and covalent manifolds of states, the alternative of all-electron calculations being rather impractical where dynamics is of interest. These conclusions are 70 Global surfaces have also been constructed effectively through ab initio methods to treat reactive dynamics in RGS. The bimolecular reaction of F 2 with ethylene is an example.…”

“…The significance of this development transcends the specifics of the system under consideration, and its broader implications are only recently being appreciated. For example, in recent test cases in such species as HF−Ar n , He−Cl 2 , Ar−Cl 2 , and HF−HF, for which detailed many-body surfaces exist, it has been demonstrated that the proper inclusion of the lowest ionic states in the DIM matrix provides a convenient means for the incorporation of nonadditivities in induction and dispersion terms to give a quantitative description of both inter- and intramolecular potential surfaces of aggregates in the ground state. − An important extension of DIM is due to Gabriel and co-workers, who showed that the basis could be used to describe truly extended electronic states, first describing the band structure of pure solids and more recently for doped solids, readdressing the nature of halogenic hole states in solid xenon …”

Excited-state site effects in luminescence spectroscopy of SH radicals in krypton matrices: Experiment and simulations

“…In a͒ spite of the long history of understanding that the properties of molecules trapped inside a matrix change due to guesthost interactions, 11 direct simulations of matrix phenomena are rather rare. [12][13][14] This is primarily due to the lack of reliable intermolecular potential energy surfaces as well as the undeveloped strategies of such modeling. However, the goals are challenging and more detailed information concerning the matrix effects is becoming available from modern spectral studies.…”