Time-dependent density functional theory as a tool for isomer assignments of hydrogen-bonded solute.solvent clusters.

Can isomer structures of hydrogen-bonded solute x solvent clusters be assigned by correlating gas-phase experimental S0 <--> S1 transitions with vertical or adiabatic excitation energies calculated by time-dependent density functional theory (TD-DFT)? We study this question for 7-hydroxyquinoline (7HQ), for which an experimental database of 19 complexes and clusters is available. The main advantage of the adiabatic TD-B3LYP S0 <--> S1 excitations is the small absolute error compared to experiment, while for the calculated vertical excitations, the average offset is +1810 cm(-1). However, the empirically adjusted vertical excitations correlate more closely with the experimental transition energies, with a standard deviation of sigma = 72 cm(-1).

Theory of High-Spin d(4) Complexes: An Angular-Overlap Model Parametrization of the Ligand Field in Vibronic-Coupling Calculations.

A new theoretical approach for the calculation of the electronic and molecular structures of octahedrally-coordinated high-spin d(4) complexes is described. A prescription for the construction of an effective (3)T1 + (5)E (O) Hamiltonian from the ligand-field matrices of a complex with general trigonal symmetry is given, where the ligand field is parametrized in terms of the angular-overlap model (AOM). The Jahn-Teller matrices for the (3)T1 + ((5)E⊗e) vibronic Hamiltonian are constructed and the lowest eigenvalues are calculated by a numerical method.

Spectral tuning by switching C-H[...]O hydrogen bonds: rotation-induced spectral shifts of 7-hydroxyquinoline HCOOH isomers.

Spectral tuning effects on visible chromophores by hydrogen bonds are central to the chemistry of vision and of photosynthesis. A model for large spectral tuning effects by hydrogen bond switching is provided by the 7-hydroxyquinoline x HCOOH complex, which forms two isomers, CTN1 and CTN2, both with an HCOOH[..

Excited-state hydrogen-atom transfer along solvent wires: water molecules stop the transfer.

Excited-state hydrogen-atom transfer (ESHAT) along a hydrogen-bonded solvent wire occurs for the supersonically cooled n = 3 ammonia-wire cluster attached to the scaffold molecule 7-hydroxyquinoline (7HQ) [Tanner, C.; et al. Science 2003, 302, 1736].