FA(I):Au+ and FA(II):Cu+ laser activity and photographic sensitization at the low coordinated surfaces of AgBr ab initio calculations

The twofold potentials of FA(I):Au+ and FA(II)Cu+ color centers at the low coordinated surfaces of AgBr thin films in providing tunable laser activity and photographic sensitization were investigated using ab initio methods of molecular electronic structure calculations. Clusters of variable size were embedded in simulated Coulomb fields that closely approximated the Madelung fields of the host surfaces, and the nearest neighbor ions to the FA defect site were allowed to relax to equilibrium in each case. Based on the calculated Stokes shifted optical transition bands and horizontal shifts along the configuration coordinate diagrams, both FA(I):Au+ and FA(II):Cu+ color centers were found to be laser active. The laser activity faded quickly as the bromide ion coordination decreased from 5 (flat) to 4 (edge) to 3 (corner) and as the size of the impurity cation increased from Cu+ to Au+. The latter relation was explainable in terms of the axial perturbation of the impurity cation. The smallest calculated Stokes‐shift at the corner surface suggested that emission had the same oscillator strength as absorption. All relaxed excited states RESs of the defect containing surfaces were deep below the lower edges of the conduction bands of the defect free ground state surfaces, indicating that FA(I):Au+ and FA(II):Cu+ are suitable laser defects. The probability of orientational destruction of the two centers attributed to the assumed RES saddle point ion configurations along the 〈110〉 axis was found to be directly proportional to the size of the impurity cation, with activation energy barriers of about 0.655–3.294 eV for Cu+, and about 1.887–3.404 eV for Au+. The possibility of exciton (energy) transfer from the sites of higher coordination to those of lower coordination is demonstrated. The more laser active FA(II):Cu+ center was more easily formed than the less laser active FA(I):Au+ center. The Glasner‐Tompkins empirical relation was generalized to include FA centers at the low coordinated surfaces of silver bromide thin film. As far as color photographic sensitization is concerned, the lowest unoccupied molecular orbitals of the selected dye molecules in the excited states were high enough for electron injection. FA defect formation and rotational diffusion of silver clusters reduced the energy gaps between the excited dye molecules and the lower edges of the conduction bands and allowed for hole injection. About 54–60% of the reduction of silver ions at the flat surface of AgBr was attributed to the host anions and FA defect formation, leaving about 40–46% for the reduction of photoelectrons as well as the electrons of the developer or dye molecules. The unrelaxed rotational diffusions of the central Ag4 by 90° decreased the latter percentage, but were severely hindered by activation energy barriers. © 2002 Wiley Periodicals, Inc. J Comput Chem 23: 1104–1120, 2002