ABSTRACT

One of the challenges in chemistry is to produce specific products from chemical reactions using light. If this objective can be achieved, a wide range of technologies would be advanced, from energy conversion (e.g., light to electricity or synthetic fuel) to chemical sensing, to general improvement of chemical process efficiency. In this project supported by the Chemical Structure, Dynamics and Mechanisms-A Program of the Division of Chemistry, Professors Marcos Dantus and Benjamin Levine of Michigan State University are using a combination of experiment and theoretical modeling to design laser light pulses that can result in specific chemical reactions. The light pulses are typically a few femtoseconds in duration (a femtosecond is one-quadrillionth of a second), and can be designed ("shaped") to contain a desired range of light wavelengths (a range of colors), or even change wavelength over the pulse duration. Depending on their shape, the light pulses affect the motions of electrons inside the molecules in different ways. Since electrons form the bonds between the atoms of a molecule, it is possible to control how the bonds break and re-form. In other words, the shape of the laser light pulses can control the outcome of chemical reactions. The graduate and undergraduate students involved in this project learn about light-matter interactions and collaborate with groups that consider these phenomena from different perspectives (spectroscopists theorists, and synthetic chemists). The researchers regularly include high school students in their research efforts and work closely with programs aimed at increasing the number of underrepresented students who pursue graduate study and research careers.

This project implements a novel strategy for achieving coherent control of the energy flow and reactivity of large organic molecules in the condensed phase. Recognizing that different electronic excited states undergo different chemical reactions, shaped laser pulses are being used to (a) populate electronic states with desirable reactivities, and (b) minimize the probability of spontaneous transition out of the desired electronic state (e.g. internal conversion). In pursuit of (b), quantum control strategies that range from semi-classical (driving the vibrational wave packet along a particular reaction coordinate) to quantum strategies with no classical analogue are being used.For example, topological effects near intersections between electronic states can be exploited to influence the reaction outcome and strong coupling, for example when potential energy surfaces are dressed by the light field. In such cases, the natural energy flow is altered and the molecular system?s coherence with the driving field can be enhanced. Advanced quantum dynamical simulations are enabling the determination of causal relationship between the structure of the initial wave packet and reaction outcomes, thus informing subsequent experiments. Successful control of internal conversion are tracked by the fluorescence yield from higher excited states. Subsequently, similar strategies are used to drive dissociative reactions in a series of dyes, which release a highly efficient fluorophore only when excited to a higher excited state. Together, this combined experimental and theoretical effort is elucidating strategies to maximize the fraction of photon energy needed to drive a condensed phase chemical reaction.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

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