The photodissociation of water in the first absorption band, H20(X) + ftoi -* H20(Á'B1) -H(1 2S) + (2 ), is a prototype of fast and direct bond rupture in an excited electronic state. It has been investigated from several perspectives-absorption spectrum, final state distributions of the products, dissociation of vibrationally excited states, isotope effects, and emission spectroscopy. The availability of a calculated potential energy surface for the Á state, including all three internal degrees of freedom, allows comparison of all experimental data with the results of rigorous quantum mechanical calculations without any fitting parameters or simplifying model assumptions. As the result of the confluence of ab initio electronic structure theory, dynamical theory, and experiment, water is probably the best studied and best understood polyatomic photodissociation system. In this article we review the joint experimental and theoretical advances which make water a unique system for studying molecular dynamics in excited electronic states. We focus our attention especially on the interrelation between the various perspectives and the correlation with the characteristic features of the upper-state potential energy surface.
Solid state gas sensors are a core enabling technology to a range of measurement applications including industrial, safety, and environmental monitoring. The technology associated with solid-state gas sensors has evolved in recent years with advances in materials, and improvements in processing and miniaturization. In this review, we examine the state-of-the-art of solid state gas sensors with the goal of understanding the core technology and approaches, various sensor design methods to provide targeted functionality, and future prospects in the field. The structure, detection mechanism, and sensing properties of several types of solid state gas sensors will be discussed. In particular, electrochemical cells (solid and liquid), impedance/resistance based sensors (metal oxide, polymer, and carbon based structures), and mechanical sensing structures (resonators, cantilevers, and acoustic wave devices) as well as sensor arrays and supporting technologies, are described. Development areas for this field includes increased control of material properties for improved sensor response and durability, increased integration and miniaturization, and new material systems, including nano-materials and nano-structures, to address shortcomings of existing solid state gas sensors.
Vibrationally mediated photodissociation of HOD, in which one photon excites an O–H stretching vibration and another photon dissociates the vibrationally excited molecule, preferentially breaks the O–H bond for some photolysis wavelengths. Excitation of the third O–H stretching overtone (4νOH ) of HOD followed by photolysis with a 239.5 or 266 nm photon produces at least 15 times more OD than OH product, as determined by laser induced fluorescence detection of both species. Dissociation of HOD(4νOH ) with a 218.5 nm photon produces comparable amounts of OH and OD fragments. This large selectivity and strong dependence on the wavelength of the photolysis photon is consistent with qualitative models of vibrationally mediated photodissociation and with recent calculations.
Experimental and theoretical studies of the photodissociation of single vibrational states in HOD provide a qualitative and quantitative understanding of the dissociation dynamics and bond selectivity of this process. Vibrationally mediated photodissociation, in which one photon prepares a vibrational state that a second photon dissociates, can selectively cleave the O–H bond in HOD molecules containing four quanta of O–H stretching excitation. Dissociation of HOD(4νOH) with 266 or 239.5-nm photons produces OD fragments in at least a 15 fold excess over OH, but photolysis of the same state with 218.5-nm photons produces comparable amounts of OH and OD. Wave packet propagation calculations on an ab initio potential energy surface reproduce these observations quantitatively. They show that the origin of the selectivity and its energy dependence is the communication of the initial vibrational state with different portions of the outgoing continuum wave function for different photolysis energies.
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