Dissociation photofragmentation

The gas phase photofragmentation of transition metal cluster complexes is discussed. The information available for the gas phase dissociation of... 

Velocity mapping has been employed in studies of 02 photophysics taking place at the one-photon [64,65], two-photon [66], and higher photon [24,25] levels. A short summary of the studies of one-photon dissociation that illustrates the importance of three-vector correlation measurements in photofragmentation of molecular oxygen will be given. Processes resulting from absorption of three or more photons will be described in more detail here since they have aspects in common with the D2 studies. 

The extremely wide range of possible dissociation energies necessitates the use of different kinds of light source to break molecular bonds. Van der Waals molecules can be fragmented with single infrared (IR) photons whereas the fission of a chemical bond requires either a single ultraviolet (UV) or many IR photons. The photofragmentation of van der Waals molecules has become a very active field in the last decade and deserves a book in itself (Beswick and Halberstadt 1993). It is a special case of UV photodissociation and can be described by the same theoretical means. In Chapter 12 we will briefly discuss some simple aspects of IR photodissociation in order to elucidate the similarities and the differences to UV photodissociation. 

In indirect photofragmentation, on the other hand, a potential barrier or some other dynamical force hinders direct fragmentation of the excited complex and the lifetime amounts to at least several internal vibrational periods. The photodissociation of CH3ONO via the 51 state is a representative example. The middle part of Figure 1.11 shows the corresponding PES. Before CH30N0(5i) breaks apart it first performs several vibrations within the shallow well before a sufficient amount of energy is transferred from the N-0 vibrational bond to the O-N dissociation mode, which is necessary to surpass the small barrier. 

Direct dissociation is the topic of this chapter while indirect photofragmentation will be discussed in the following chapter. Both categories are investigated with the same computational tools, namely the exact solution of the time-independent or the time-dependent Schrodinger equation. The underlying physics, however, differs drastically and requires different interpretation models. Direct dissociation is basically a classical process while indirect dissociation needs a fully quantum mechanical description. 

In contrast to indirect dissociation, which is the topic of Chapter 7, direct photodissociation is relatively simple to understand. The reflection principle describes qualitatively the fully state-resolved photofragmentation cross sections a E, n, j) as a multi-dimensional mapping of the initial coordinate distribution in the electronic ground state ... 

Fig. 7.7. Comparison of the different energy behavior of partial dissociation cross sections a(E,j) for the production of NO(j) in indirect, HONO(iS i), and in direct, ClNO(Si), photofragmentation. Note the quite different energy scales The results for HONO are obtained from a two-dimensional model (Schinke, Untch, Suter, and Huber 1991) and the cross sections for C1NO are taken from a three-dimensional wavepacket calculation (Untch, Weide, and Schinke 1991b).

Bruno, A.E., Briihlmann, U., and Huber, J.R. (1988). Photofragmentation LIF spectroscopy of NOCL at dissociation wavelengths > 450 nm. Parent electronic spectrum and spin state and A-doublet populations of nascent NO and CL fragments, Chem. Phys. 120, 155-167. 

Shapiro, M. (1986). Photophysics of dissociating CH3I Resonance-Raman and vibronic photofragmentation maps, J. Phys. Chem. 90, 3644-3653. 

The general theory for the absorption of light and its extension to photodissociation is outlined in Chapter 2. Chapters 3-5 summarize the basic theoretical tools, namely the time-independent and the time-dependent quantum mechanical theories as well as the classical trajectory picture of photodissociation. The two fundamental types of photofragmentation — direct and indirect photodissociation — will be elucidated in Chapters 6 and 7, and in Chapter 8 I will focus attention on some intermediate cases, which are neither truly direct nor indirect. Chapters 9-11 consider in detail the internal quantum state distributions of the fragment molecules which contain a wealth of information on the dissociation dynamics. Some related and more advanced topics such as the dissociation of van der Waals molecules, dissociation of vibrationally excited molecules, emission during dissociation, and nonadiabatic effects are discussed in Chapters 12-15. Finally, we consider briefly in Chapter 16 the most recent class of experiments, i.e., the photodissociation with laser pulses in the femtosecond range, which allows the study of the evolution of the molecular system in real time. 

The first quantitative measurement of the distribution of excited atomic states produced in the multiphoton dissociation of a metal carbonyl has been made for Cr(CO)6. Photodissociation does not yield spin- or parity-differentiated states, rather the state distribution appears to be statistical. Photofragmentation dynamics of Cr(CO)6 in the gas phase have been measured and two channels of dissociation revealed. One of these is a rapid predissociation (efficiency 36%) and the other a slow process (efficiency... 

Other Photofragmentations - Photodissociation of tert-huty hydroperoxide at 266 nm gives OH radicals with dynamics which are similar to those found for OH from H2O2, and which are consistent with dissociation via a repulsive excited state. Rates of p-scission of the ter/-butoxy radical to acetone and methyl radicals have been determined in flash-photolysis experiments by monitoring its transient UV absorption and its laser-induced fluorescence. ... 

The rotational distribution of CN produced by this reaction at 193 nm has been measured and fitted to a Boltzmann distribution with T = 1450 K [74], Combined with photofragmentation translational spectroscopy, it was initially concluded that this channel is formed by an impulsive dissociation through a repulsive excited state [72],... 

Photodissociation involves a direct optical excitation (usually in the UV or VUV region) from the ground (bound) electronic state to the excited (repulsive) electronic state of the molecule which then dissociates. The fundamental quantity in photofragmentation calculation is the Franck-Condon (FC) factor... 

An elegant molecular-beam study of the photofragmentation of aryl halides and methyl iodide has permitted extraction of excited-state lifetimes from a measured anisotropy parameter which depends upon the lifetime of excited state, the rotational correlation time of the molecule, and the orientation of the electronic transition dipole with respect to the —X bond.38 The lifetimes obtained were methyl iodide 0.07 ps, iodobenzene 0.5 ps, a-iodonaphthalene 0.9 ps, and 4-iodobiphenyl 0.6 ps, from which it was concluded that, whereas methyl iodide dissociates directly, the aryl halides predissociate. A crossed-beam experiment using electron-beam excitation has yielded the results for the Si Tt intersystem-crossing relaxation time in benzene, [sHe]benzene, fluorobenzene, and... 

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