Theoretical Study of 8-hydroxyquinoline Derivatives as Potential Antennas in Lanthanide complexes: Photophysical Properties and Elucidation of Energy Transfer Pathways.

A series of 8-hydroxyquinoline derivatives were characterized and tested as potential antennas in a set of designed lanthanide complexes. The molecular structure and ligand localized nature of the excited states were studied in the framework of the multiconfigurational methods CASSCF/NEVPT2 combined with TDDFT- based approaches, which allows applying a fragmentation scheme in the analysis of the most probable sensitization pathway via antenna effect. The photophysical properties of all the complexes and antennas were carefully analyzed, and the most probable energy transfer pathways were elucidated. Rate constants for photophysical processes involved in the mechanism were calculated, showing a significant contribution of the vibronic coupling in all cases and the predominant intersystem-crossing between S1 and T1 states was demonstrated from the analysis of the nature of the wave function of those states. The energy transfer process described herein demonstrates the possibility of Eu(III) and Nd(III) sensitization by the studied ligands. The proposed methodology gives a complete picture of the antenna excited state dynamics.

CASPT2, CASSCF and non-adiabatic molecular dynamics (NAMD) studies on the low-lying electronic states of 1H-1,2,3-triazole photolysis

The photolysis mechanisms of 1H-1,2,3-triazole and 1H-1,2,3-benzotriazole were elucidated by employing multiconfigurational methods (CASSCF and CASPT2) and non-adiabatic molecular dynamics.

Ab initio electronic structure study of a model water splitting dimer complex

The electronic structure of a model Mn dimer is examined during the water splitting mechanism using multiconfigurational methods.

Resonant Raman spectra of molecules with diradical character: multiconfigurational wavefunction investigation of neutral viologens

In search for a relationship between the diradical character and resonance Raman signatures of neutral viologens by multiconfigurational methods.

Theoretical prediction on the structures of the HMgN- and HNMg- anions using multiconfigurational methods

The nine-valence-electron HMgN- and HNMg- anions have been investigated for the first time theoretically using CASSCF (complete active space self-consistent field) and CASPT2 (multiconfiguration second-order perturbation theory) methods in conjunction with the contracted atomic natural orbital (ANO) basis sets. The structures of the low-lying electronic states of HMgN- and HNMg- were predicted. The possible unimolecular conversions between HMgN- and HNMg-were discussed. The calculated results indicated that the ground-state of HMgN-is linear, while the ground-state HNMg- is bent, which is in contradiction to Walsh?s rules predicting linear structures for the HXY systems containing 10 or less valence electrons.

A theoretical study of three gas-phase reactions involving the production or loss of methane cations

Three reactions paths involving methane cation were studied by multiconfigurational methods and the rate coefficients and Arrhenius parameters were obtained.