Disorder-to-order transition of 1,4-dimethylnaphthalene: Formation of molecular complex with water and p-xylene on Al2O3 (0001).

Amorphous 1,4-dimethylnaphthalene, DMN, that can be prepared by vacuum deposition on Al2O3 exhibits relatively intense excimer fluorescence. Upon heating the surface, the adlayer undergoes a disorder-to-order transition, signaled by a decrease in excimer and an increase in monomer fluorescence. In a bilayer experiment, water, which has a lower desorption temperature than DMN, is vacuum deposited first, followed by DMN. When the surface is heated, water percolates through the DMN and forms a molecular H2O-DMN surface complex that desorbs simultaneously. The stoichiometric ratio of this complex was determined to be (DMN)(1.4+/-0.3).H2O. When the bilayer was formed with p-xylene, a complex of DMN-p-xylene was observed that had the stoichiometry of (DMN)(7.9+/-1).p-xylene.

Electronic energy transfer in benzophenone adlayer.

The extent to which energy transfer occurs in electronically excited organic adlayer films on dielectric surfaces is investigated. Migration and subsequent trapping of the energy in the film are observed by pumping the singlet state of an organic adlayer of benzophenone and by monitoring the phosphorescence and fluorescence lifetimes. To observe the effects of adsorption, benzophenone was chosen as the adlayer because the energies of its well characterizedn,π carbonyl states are remarkably sensitive to solvent interactions. Upon excitation with a nitrogen laser, the perturbation on the electronic states of benzophenone by the substrate caused the emergence of the normally absent fluorescence from the adlayer traps at the interface between the surface of the dielectric substrate and the adlayer. Energy transfer to this interface was observed as a function of film thickness. On the surface of a single crystal of an organic crystal, naphthalene, energy transfer from the adlayer to the substrate was observed, whereas such transfer was not energetically possible with the other dielectric surfaces.

A microprocessor-controlled photon counter for pulsed optically detected magnetic resonance.

In pulsed optically detected magnetic resonance (ODMR) spectroscopy, a lock-in amplifier is used to monitor the signal which is phase-matched to the duty cycle of an applied sequence of pulses. However, since the desired signals reside atop a much larger amplitude-modulated signal, lock-in amplification methods are difficult to use. Commerically available photon counters are of limited use, because the pulsed ODMR method requires sequential counting over several time intervals, often with minimum time delay between the intervals. The multiaccumulator photon counter described here is capable of such sequential counting over as many as four intervals. The microprocessor which controls the counter algebraically manipulates the photon counts during each of the duty cycles. The result is an inexpensive yet versatile photon counter which is suited for pulsed ODMR and other applications in which sequential counting is necessary.

Triplet state energy transfer in several proteins.

Energy transfer between excited triplet states of aromatic amino acid residues was observed at 1.4 degrees K. The distance necessary for energy transfer between monomeric tyrosine and tryptophan residues was determined to be roughly 63 A. Total phosphorescence decay rate constants for several proteins were determined while emission corresponding to tyrosine and tryptophan residues was monitored. The observed decay rate constants are interpreted in terms of intramolecular interactions of the polypeptide residues.

A study of solvent effects on the phosphorescence properties of flavins.

A combination of zero field triplet state techniques are used to study the excited electronic states of a series of flavin and flavin related molecules both in single crystals and glass matrices. Particular attention is given to the effects of solvent interaction on the triplet state properties of the flavin molecules. The total phosphorescence decay rate constants at 1.4 degrees K are reported for the flavin molecules in polar and nonpolar solvents. The rate constants are then correlated to the degree of solvent interaction. Results indicate possible complex formation between the isoalloxazine and adenine groups in FAD. Finally, the results and possible interpretation on the study of a flavoenzyme, L-amino acid oxidase are presented.