Intermediate excited state

Excitation to produce a diradical-like intermediate (excited state) can result in either hydrogen abstraction or rearrangement and closure to form the cyclobutene ... 

Alpha particles are composed of two protons and two neutrons. Thus they have Z = 2, N = 2, and A = 4 and correspond to a helium nucleus He. The emission of a particles thus produces a decrease of 4 units in A. An unstable nuclide undergoing a decay may emit a particles of various energy and thus directly reach the ground level of the stable product. Alternatively, as in )3 emission, an intermediate excited state is reached, followed by y emission. Figure 11.7 shows, for example, the decay process of ioTh., which may directly attain the ground level of by emission of a particles of energy 5.421 MeV or intermediate excited states by emission of a particles of lower energy, followed by y emission. 

Progress in photochemistry could only be made following progress in spectroscopy and, in particular, the interpretation of spectra in at least semiquantitative terms, but history has shown that this was not enough. The arrival of new methods of analysis which permit determination of small amounts of products, the development of flash photolysis, nuclear magnetic resonance, and electron spin resonances which can yield valuable information about the natures of intermediate excited states, as well as of atoms and radicals, all have permitted the photochemist to approach the truly fundamental problem of photochemistry What is the detailed history of a molecule which absorbs radiation ... 

In the experiments described thus far, the pump laser simply populates the intermediate excited state. The consequence is that the experiment becomes a means to study that excited state. Often we are more concerned with learning about the ground state than about excited states. For this purpose, it is useful to prepare a vibrational wavepacket of that ground state. One useful means to do this is to excite the species of interest to an allowed excited state and then to down-pump from that excited state back to the ground state, with a pulse that generates a packet rather than a stationary state. The simplest way to do this currently seems to be to raise the power level of the pulsed pump laser [26]. This process is shown schematically in Fig. 7. 

Fourth, coherent excitation by means of femtosecond laser pulses of a controllable pulse interval makes it possible to control to some extent the coherent evolution of molecules in an intermediate excited state and... 

The evidence for such a mechanism results from both the reaction stereochemistry and also from the observation of minor diphenyltoluene by-products (Scheme 8). The major pathway is outlined using heavy arrows. This can be seen to afford the stereospecificity of equations 14a and 14b. Additionally, each of the diradical intermediates and intermediate excited states—B, C, E, F and G—undergo a minor extent of internal bond fission [i.e. Grob or 2,3- (1,4) fragmentation] to afford a diphenyltoluene with the corresponding ring skeleton. The basis for the choice of a main pathway versus the minor ones comes from the observed stereochemistry. 

Figure 1 Schematic energy diagram for the DIET process due to the MGR model illustrating the relaxation and desorption processes. Electronic excitation due to laser irradiation occurs via the Franck-Condon transition. After a residue time t at the intermediate excited state, relaxation occurs with an excess energy ZA surpassing the surface barrier for desorption. The value of depends strongly on t, and no desorption occurs when t is shorter than the critical residence time tc. The Absicissa is the adsorbate-substrate distance.

Figure 2 Schematic energy diagram representing the DIET process due to Antoniewicz model, in which the intermediate excited state is a negative ion. The parameters are similar to those given in Fig. 1. The Absicissa is the adsorbate-substrate distance.

The rotational and the translational freedom appear after desorption of adsorbed molecules and each energy is kept without any disturbance before detection in the present experimental condition, since there is no collision and the lifetime of the excited states for a desorbed molecule is long. The experimental data can be analyzed by a simple model using the impulse scheme, con fi ned to the momentum transferred from the substrate to an adsorbate atom, in which the form of the excited-state PES and the transition process need not be assumed [68, 69]. The energy released from the excited state is converted to the momentum and this energy is transferred impulsively. The desorption also occurs impulsively. This simple model sheds hght on the property of the intermediate excited state, and the intermediate excited state plays an important role in the DIET process. 

The impulse model is applied to the interpretation of experimental results of the rotational and translational energy distributions and is effective for obtaining the properties of the intermediate excited state [28, 68, 69], where the impulse model has widely been used in the desorption process [63-65]. The one-dimensional MGR model shown in Fig. 1 is assumed for discussion, but this assumption does not lose the essence of the phenomena. The adsorbate-substrate system is excited electronically by laser irradiation via the Franck-Condon process. The energy Ek shown in Fig. 1 is the excess energy surpassing the dissociation barrier after breaking the metal-adsorbate bond and delivered to the translational, rotational and vibrational energies of the desorbed free molecule. 

This relation indicates that the residence time t is approximately proportional to the rotational quantum number J in the classical limit. On the other hand, the lifetime t in the intermediate excited state of the desorbing molecule is defined by the relation of... 

Table 5 Estimated lifetime (t) and critical residence time (tc) in the intermediate excited state for NO desorption of hep hollow species from Pt(l 11).

Finally, we would like to make a scenario of the desorption activity for NO and CO desorption from Pt(l 1 1) and Pt(l 1 1)-Ge surface alloy. This scenario will be extended to a general concept of desorption in the DIET process of simple molecules from metal surfaces. The lifetime and the critical residence time in the intermediate excited state followed by desorption are important keys for solving what is the origin of the desorption activity in the DIET process from metal surfaces. The excited molecules are not desorbed, if the residence time in the excited state is shorter than the critical residence... 

The rotational temperature obtained from a linear relation in the Boltzmann plot of the rotational energy distribution is an index of the lifetime in the intermediate excited state and decreases with decreasing lifetime. The rotational temperature of CO desorbed from Pt(l 1 1) is very low as compared with that of NO desorption, i.e. the lifetime of the excited CO is supposed to be much shorter than that of NO. In the case of CO desorption from Pt(l 11), however, the lifetime is not obtained from the rotational energy distribution, since desorbed molecules are detected by the (2 + 1 )REMPI method in the experiment [ 12] and then the single rotational states are not resolved. On the other hand, the rotational temperature of NO desorbed from Pt(l 1 1)-Ge surface alloy is lower than that from Pt(l 1 1). Then, it is speculated that the lifetime of the excited CO on the alloy is shorter than that on Pt( 111) and the residence time of the excited CO on the alloy is too short to be desorbed. As a consequence, the excited CO molecules are recaptured in the relaxation without desorption. However, it has not been understood why the lifetime of the excited CO molecule (or the excited CO-Pt complex) on Pt( 1 1 1) is shorter than that of the excited NO molecule (complex) on Pt(l 11), and further on the Pt-Ge alloy as compared with Pt(l 1 1). 

The Raman spectra are quicker and easier to determine than the infrared absorption spectra because ordinary optical equipment can be used, but frequently they are more difficult to interpret. The quantum restrictions in the two phenomena, particularly for symmetrical molecules, are not always the same, because the Raman spectrum involves an intermediate excited state of the molecule. For this reason, it is desirable to have the data of both Raman and infrared absorption spectra in order to determine completely the rotational and rotational-vibrational energy levels in the molecule. The Raman spectrum can be obtained in some solutions where direct absorption measurements are impossible because the solvent is opaque in the infrared. Aqueous solutions offer a good example of such a case. 

The surfaces of dust grains serve as catalysts for many reactions that do not proceed efficiently in the gas phase, in particular those involving intermediate excited-state complexes (e.g. radiative association). The most notable example is the formation of molecular hydrogen, which occurs almost entirely on dust surfaces (e.g. Hollenbach Salpeter 1971 Watson Salpeter 1972). It is assumed that a... 

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