Michael Kasha

Bio: Michael Kasha is an academic researcher from Florida State University. The author has contributed to research in topics: Excited state & Spectroscopy. The author has an hindex of 47, co-authored 97 publications receiving 12285 citations.

The exciton model in molecular spectroscopy

Abstract: The molecular exciton model has received its most extensive development and application in the field of molecular crystals1'2. More recently, numerous applications to non-crystalline molecular composite systems have been made, including van der Waals and hydrogen-bonded dimers, trimers, and higher order aggregates. Another type of composite system has also been investigated, namely the composite molecule consisting of covalently bonded molecular units, with intrinsic individual unsaturated electronic systems so isolated by single bonds that but little or insignificant electronic overlap between units may occur. It is now well established that in molecular aggregates and in composite molecules, exciton effects may be observed if sufficiently strong electronic transitions exist in the component sub-units. The result of exciton splitting of excited states in the composite molecule may be the appearance of strong spectral shifts or splittings (which may be of the order of 2000 cm—1) of the absorption bands for the component molecules. At the same time, as a consequence of the exciton splitting of the excited state manifold, an enhancement of triplet state excitation may result. The purpose of this paper is to present a summary of the various type cases for molecular dimers, trimers and double and triple molecules in the description of the molecular exciton strong-coupling model. Then it will be shown by new experimental examples that, even in those cases where no significant exciton effect is observable in the singlet—singlet absorption spectrum for the composite molecule (intermediate and weak coupling cases), the enhancement of lowest triplet state excitation may still be conspicuous and significant. The ideas which are summarized in this paper have a curious history. Long ago, Kautsky and Merkel3 demonstrated experimentally that aggregation of dyes facilitated their action as photophysical sensitizers in photochemical reactions, at the same time diminishing their fluorescence efficiency. Kautsky attributed these easily demonstrated effects to enhancement of metastable state excitation in the aggregate dye. There is no doubt today that the metastable state he described is the lowest triplet state of the molecules studied. However, he did not distinguish between intrinsic and enhanced metastable (triplet) state excitation, so his interpretations were largely overlooked. Forster in l946 used the quasi-classical vector model to

Energy transfer mechanisms and the molecular exciton model for molecular aggregates.

Abstract: Energytransferphenomenacontinuetofascinatethebiologist, chemist, and physicist, and the literature contains numerous experiments designed to demonstrate the presence of excitation energy transfer. At the present stage of development of the theoryofsuchprocesses, thegoal oftheseresearchesmightwell be not merely the demonstration of the presence of energy transfer, but a more detailed investigation designed to establish which available mechanism of energy transfer is operative. The field of excitation energy transfer is replete with redundant and overlapping terms, whose multitude itself lends little order to the subject. Various authors quote, as energy transfer mechanisms, exciton transfer, resonance transfer, dipole-dipole transfer, inductive resonance, resonance force transfer, virtual photons, and diffuse excitation, among others. This paper will be devoted to the laying down of a further perspective for the discrimination and understanding of the main types of excitation energy transfer. A necessary

Collisional Perturbation of Spin‐Orbital Coupling and the Mechanism of Fluorescence Quenching. A Visual Demonstration of the Perturbation

Abstract: A yellow color is produced when two colorless pure liquids, α‐chloronaphthalene and ethyl iodide, are mixed, although no chemical reaction occurs. Spectroscopic examination reveals that the lowest singlet→triplet absorption band of the naphthalene molecule is greatly enhanced in intensity in the presence of the iodide, and that the development of this absorption band is responsible for the color effect. The process is interpreted in terms of a collisional perturbation of spin‐orbital coupling in the π‐electron orbitals of the naphthalene. The significance of this phenomenon in several topics in spectroscopy and chemistry is discussed. In particular, the molecular mechanism of heavy atom quenching of fluorescence by foreign species is resolved. A novel Beer's law anomaly is predicted for intercombinations.

Principles of fluorescence spectroscopy

Abstract: Fluorescence methods are being used increasingly in biochemical, medical, and chemical research. This is because of the inherent sensitivity of this technique. and the favorable time scale of the phenomenon of fluorescence. 8 Fluorescence emission occurs about 10- sec (10 nsec) after light absorp tion. During this period of time a wide range of molecular processes can occur, and these can effect the spectral characteristics of the fluorescent compound. This combination of sensitivity and a favorable time scale allows fluorescence methods to be generally useful for studies of proteins and membranes and their interactions with other macromolecules. This book describes the fundamental aspects of fluorescence. and the biochemical applications of this methodology. Each chapter starts with the -theoreticalbasis of each phenomenon of fluorescence, followed by examples which illustrate the use of the phenomenon in the study of biochemical problems. The book contains numerous figures. It is felt that such graphical presentations contribute to pleasurable reading and increased understand ing. Separate chapters are devoted to fluorescence polarization, lifetimes, quenching, energy transfer, solvent effects, and excited state reactions. To enhance the usefulness of this work as a textbook, problems are included which illustrate the concepts described in each chapter. Furthermore, a separate chapter is devoted to the instrumentation used in fluorescence spectroscopy. This chapter will be especially valuable for those perform ing or contemplating fluorescence measurements. Such measurements are easily compromised by failure to consider a number of simple principles."

Aggregation-Induced Emission: Together We Shine, United We Soar!

Abstract: Ju Mei,†,‡,∥ Nelson L. C. Leung,†,‡,∥ Ryan T. K. Kwok,†,‡ Jacky W. Y. Lam,†,‡ and Ben Zhong Tang*,†,‡,§ †HKUST-Shenzhen Research Institute, Hi-Tech Park, Nanshan, Shenzhen 518057, China ‡Department of Chemistry, HKUST Jockey Club Institute for Advanced Study, Institute of Molecular Functional Materials, Division of Biomedical Engineering, State Key Laboratory of Molecular Neuroscience, Division of Life Science, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China Guangdong Innovative Research Team, SCUT-HKUST Joint Research Laboratory, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China

Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers

Abstract: A dye that both maximizes electrolyte compatibility and improves light-harvesting properties has been designed for dye-sensitized solar cells. In cells based on the cobalt(II)/(III) redox mediator, use of the dye resulted in a power-conversion efficiency of 13%, revealing the great potential of porphyrin dyes for future solar cell applications.

Organic Photoredox Catalysis

Abstract: In this review, we highlight the use of organic photoredox catalysts in a myriad of synthetic transformations with a range of applications. This overview is arranged by catalyst class where the photophysics and electrochemical characteristics of each is discussed to underscore the differences and advantages to each type of single electron redox agent. We highlight both net reductive and oxidative as well as redox neutral transformations that can be accomplished using purely organic photoredox-active catalysts. An overview of the basic photophysics and electron transfer theory is presented in order to provide a comprehensive guide for employing this class of catalysts in photoredox manifolds.