Photodissociation diatomic

Photodissociation of a linear triatomic such as [85, 86] or Hgl2 [8] to produce a vibrationally excited diatomic, or cage recombination of a photodissociated diatomic such as I2 [78, 81] are classic model simple systems for reaction dynamics. Here we discuss tire Hgl2—>HgI + I reaction studied by Hochstrasser and co-workers [87, 88 and 89]. 

Figure C3.5.7. Possible modes of vibrational wavepacket (smootli Gaussian curve) motion for a highly vibrationally excited diatomic molecule produced by photodissociation of a linear triatomic such as Hglj, from [8].

The general principle of detection of free radicals is based on the spectroscopy (absorption and emission) and mass spectrometry (ionization) or combination of both. An early review has summarized various techniques to detect small free radicals, particularly diatomic and triatomic species.68 Essentially, the spectroscopy of free radicals provides basic knowledge for the detection of radicals, and the spectroscopy of numerous free radicals has been well characterized (see recent reviews2-4). Two experimental techniques are most popular for spectroscopy studies and thus for detection of radicals laser-induced fluorescence (LIF) and resonance-enhanced multiphoton ionization (REMPI). In the photochemistry studies of free radicals, the intense, tunable and narrow-bandwidth lasers are essential for both the detection (via spectroscopy and photoionization) and the photodissociation of free radicals. 

Hydroxyl radical (OH) is a key reactive intermediate in combustion and atmospheric chemistry, and it also serves as a prototypic open-shell diatomic system for investigating photodissociation involving multiple potential energy curves and nonadiabatic interactions. Previous theoretical and experimental studies have focused on electronic structures and spectroscopy of OH, especially the A2T,+-X2n band system and the predissociation of rovibrational levels of the M2S+ state,84-93 while there was no experimental work on the photodissociation dynamics to characterize the atomic products. The M2S+ state [asymptotically correlating with the excited-state products 0(1 D) + H(2S)] crosses with three repulsive states [4>J, 2E-, and 4n, correlating with the ground-state fragments 0(3Pj) + H(2S)[ in... 

In spite of the fact that in alkali vapors, which contain about 1 % diatomic alkali-molecules at a total vapor-pressure of 10 torr, the atoms cannot absorb laser lines (because there is no proper resonance transition), atomic fluorescence lines have been observed 04) upon irradiating the vapor cell with laser light. The atomic excited states can be produced either by collision-induced dissociation of excited molecules or by photodissociation from excited molecular states by a second photon. The latter process is not improbable, because of the large light intensities in the exciting laser beam. These questions will hopefully be solved by the investigations currently being performed in our laboratory. 

Figure 4.34 compares the absorption spectra of the diatomic halogens, F2, Cl2, Br2, and I2. Cl2 is of particular recent interest in the troposphere in that levels up to 150 ppt have been observed in marine areas (Keene et al., 1993 Pszenny et al., 1993 Spicer et al., 1998). Table 4.30 summarizes the absorption cross sections of Cl2, Br2, and BrCl (DeMore et al., 1997 Marie et al., 1994 Hubinger and Nee, 1995). These diatomics all dissociated with a photodissociation quantum yield of 1 (Calvert and Pitts, 1966). 

The examples gathered here deal primarily with relatively simple organic reactions, though the photodissociation of one inorganic diatomic molecule is included as an historically important paradigmatic process. The examples cover but a fraction of the field, but may serve to illustrate the powers and limitations of the area at its present state of development. 

Unlike the case of simple diatomic molecules, the reaction coordinate in polyatomic molecules does not simply correspond to the change of a particular chemical bond. Therefore, it is not yet clear for polyatomic molecules how the observed wavepacket motion is related to the reaction coordinate. Study of such a coherent vibration in ultrafast reacting system is expected to give us a clue to reveal its significance in chemical reactions. In this study, we employed two-color pump-probe spectroscopy with ultrashort pulses in the 10-fs regime, and investigated the coherent nuclear motion of solution-phase molecules that undergo photodissociation and intramolecular proton transfer in the excited state. 

R. D. Levine The coherence that is being discussed by Profs. Troe and Zewail is due to a localized vibrational motion in the AB diatomic product of a photodissociation experiment ABC — AB + C. Such experiments have been done both for the isolated ABC molecule and for the molecule in an environment. As the fragments recede, effective coupling of the AB vibrational motion to the other degrees of freedom can rapidly destroy the localized nature of the vibrational excitation. 

Photoionization is a special case of a two-body dissociation where Me Ma. thus, the photoelectron receives essentially all of the KER and the atom or molecule (e.g., from a photodissociation event) essentially retains its initial velocity as it is ionized. For photodissociation of a homonuclear diatomic the KER is equally shared between the two product atoms (A and A ). The sum of the internal energies in the product atoms can be determined from the measured KER (l/2mAVA + l/2mA.VA) and from... 

One of the earliest models is the quasi-diatomic model (10-13). This model is based on the assumption that the normal modes describing the state(s) of the photofragments are also the normal modes of the precursor molecule. This means, for example, that in the photodissociation of a linear triatomic molecule ABC A + BC (e.g., photodissociation of ICN - I + CN), the diatomic oscillator BC is- assumed to be a normal mode vibration in the description of the initial state of the triatomic molecule ABC. This means that the force constant matrix describing the vibrational motion of the molecule ABC can be written in the form (ignoring the bending motion) ... 

In the following we will call the a u,n,j) partial photodissociation cross sections.t They are the cross sections for absorbing a photon with frequency u and producing the diatomic fragment in a particular vibrational-rotational state (n,j). Partial dissociation cross sections for several photolysis frequencies constitute the main body of experimental data and the comparison with theoretical results is based mainly on them. Summation over all product channels (n,j) yields the total photodissociation cross section or absorption cross section ... 

The vector of the electromagnetic field defines a well specified direction in the laboratory frame relative to which all other vectors relevant in photodissociation can be measured. This includes the transition dipole moment, fi, the recoil velocity of the fragments, v, and the angular momentum vector of the products, j. Vector correlations in photodissociation contain a wealth of information about the symmetry of the excited electronic state as well as the dynamics of the fragmentation. Section 11.4 gives a short introduction. Finally, we elucidate in Section 11.5 the correlation between the rotational excitation of the products if the parent molecule breaks up into two diatomic fragments. 

Up to now we have exclusively considered the scalar properties of the photodissociation products, namely the vibrational and rotational state distributions of diatomic fragments, i.e., the energy that goes into the various degrees of freedom. Although the complete analysis of final state distributions reveals a lot of information about the bond breaking and the forces in the exit channel, it does not completely specify the dissociation process. Photodissociation is by its very nature an anisotropic process — the polarization of the electric field Eo defines a unique direction relative to which all vectors describing both the parent molecule and the products can be measured. These are ... 

Fig. 7.2.3 A true unimolecular reaction here photodissociation of a diatomic molecule.

Let us consider some experimental studies. Developing practically the idea proposed as early as 1968 by van Brunt and Zare (see [176, 376] for a review), a number of authors [232, 328, 383] investigated fluorescence polarization on atomic photofragments excited in the process of photodissociation of the simplest diatomic molecules. Observation of linear polarization (of the order of V 0.05) in the fluorescence of Na(2P3/2) atoms after the photodissociation of Na2 molecules is reported in [328]. Detailed studies of photodissociation of K2 through the transition —> BlHu... 

In order to demonstrate the efficiency and robustness of the formulations presented in Sect. 5.2 and 5.3, three practical applications are considered here. In the first part of this section, we consider the complete excitation of a wavepacket from a nonequilibrium displaced position, which is directly related to the idea of bond-selective breaking, as explained in the Introduction . This is demonstrated numerically by taking diatomic molecules LiH and NaK as examples. In the second part, we consider the complete pump-dump control and creation of a localized wavepacket using quadratic chirping within the pump-dump mechanism. The bond-selective photodissociation of the H20 molecule is discussed in the third part of this subsection as an example of a multidimensional system. 

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