Highly vibrationally excited molecules often control the course of chemical reactions in the atmosphere, combustion, plasmas, and many other environments. The research described in this Progress Report uses laser excitation and interrogation techniques to study and control the dynamics of highly vibrationally excited molecules. In particular, they show that it is possible to unravel the details and influence the course of photodissociation and bimolecular reaction. The experiments use laser excitation of overtone vibrations to prepare highly vibrationally excited molecules, frequently with single quantum state resolution, and laser spectroscopy to monitor the subsequent behavior of the excited molecule. We have studied the vibrationally mediated photodissociation and the bond- and state-selected bimolecular reaction of highly vibrationally excited molecules. In the first process, one photon creates a highly excited molecule, a second photon from another laser dissociates it, and light from a third laser detects the population of individual product quantum states. This approach allows us to explore otherwise inaccessible regions of the ground and excited state potential energy surface and, by exciting to the proper regions of the surface, to control the breaking of a selected chemical bond. In the second process, the highly vibrationally excited molecule reacts with an atom formed either in a microwave discharge or by photolysis and another laser interrogates the products. We have used this approach to demonstrate mode- and bond-selected bimolecular reactions in which the initial excitation controls the subsequent chemistry. 30 refs., 8 figs.

Highly vibrationally excited molecules often control the course of chemical reactions in the atmosphere, combustion, plasmas, and many other environments. The research described in this Progress Report uses laser excitation and interrogation techniques to study and control the dynamics of highly vibrationally excited molecules. In particular, they show that it is possible to unravel the details and influence the course of photodissociation and bimolecular reaction. The experiments use laser excitation of overtone vibrations to prepare highly vibrationally excited molecules, frequently with single quantum state resolution, and laser spectroscopy to monitor the subsequent behavior of the excited molecule. We have studied the vibrationally mediated photodissociation and the bond- and state-selected bimolecular reaction of highly vibrationally excited molecules. In the first process, one photon creates a highly excited molecule, a second photon from another laser dissociates it, and light from a third laser detects the population of individual product quantum states. This approach allows us to explore otherwise inaccessible regions of the ground and excited state potential energy surface and, by exciting to the proper regions of the surface, to control the breaking of a selected chemical bond. In the second process, the highly vibrationally excited molecule reacts with an atom formed either in a microwave discharge or by photolysis and another laser interrogates the products. We have used this approach to demonstrate mode- and bond-selected bimolecular reactions in which the initial excitation controls the subsequent chemistry. 30 refs., 8 figs.

The goal of this Department of Energy sponsored research is to discover the properties, behavior, and dissociation dynamics of vibrationally energized molecules, which are crucial participants in many chemical reactions. The authors study vibrationally energized molecules by using an optical excitation scheme to prepare them and a subsequent photon to dissociate them into fragments that they detect with a spectroscopic probe. This technique, vibrationally mediated photodissociation, provides new information on vibrationally energized molecules and even provides a means of controlling the course of a molecular decomposition. During the most recent period of Department of Energy support, the authors have advanced this work in three directions: they have used vibrational overtone excitation to control the decomposition pathways in the tetra-atomic molecule isocyanic acid (HNCO) and unravelled the decomposition pathways in hydroxylamine (NH2OH), they have implemented stimulated Raman excitation as the vibrational state preparation technique in vibrationally mediated photodissociation, and they have tested the limits of transient grating spectroscopy as a means of obtaining electronic spectra of vibrationally excited molecules.

Combined vibrational overtone excitation and laser induced fluorescence detection was used to study dissociation dynamics of hydroxylamine (NH2OH), laser induced grating experiments on water were analyzed, discovering the important role that electrostriction and thermal relaxation play, and a new apparatus for preparing vibrationally excited molecules with simulated Raman excitation was completed and the first measurements made. Role of vibrational excitation in photodissociation dynamics was studied using a vibrational state preparation technique, such as vibrational overtone excitation or stimulated Raman excitation, to create molecules with particular nuclear motions and then excite that molecule to a dissociative electronic state. Because the vibrational excitation alters the dissociation dynamics in the excited state, both by providing access to different portions of the excited state surface and by altering the motion of the system on the surface, it is usually refered to as vibrationally mediated photodissociation.

We have used combined vibrational overtone excitation and laser induced fluorescence detection to study dissociation dynamics of hydroxylamine (NH2OH), have performed our first laser induced grating experiments on water, and have begun assembling a new apparatus for preparing vibrationally excited molecules with simulated Raman excitation. We study role of vibrational excitation in photodissociation dynamics by using a vibrational state preparation technique, such as vibrational overtone excitation or stimulated Raman excitation, to create molecules with particular nuclear motions and then to excite that molecule to a dissociative electronic state.