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Absorption spectra electron transitions

Indirect photodissociation involves two more or less separate steps the absorption of the photon and the fragmentation of the excited complex. Resonances, which mirror the quasi-bound states of the intermediate complex in the upper electronic state, are the main features. They have an inherently quantum mechanical origin. If we consider — in very general terms — the inner region, before the fragments have obtained their identities, as the transition state, then the resolution of resonance structures in the absorption spectrum manifests transition state spectroscopy in the original sense of the word (Foth, Polanyi, and Telle 1982 Brooks 1988). [Pg.173]

To determine the excitation energy of the lowest electronic level the contributions in the absorption spectrum from transitions to different vibrational modes of the excited state have to be separated. In the deconvolution of the absorption spectra Gaussian line shapes are assumed for the transitions to the different vibrational levels. The analysis leads to the transition wavelength A00 for the excitation from the ground state to the zero vibrational level of the excited state. [Pg.174]

The visible-UV absorption spectrum of transition metal complexes is characterized by a high density of various electronic excited states (Metal-Centred, Metal-to-Ligand-Charge-Transfer, Ligand-to-Ligand-Charge-Trans-... [Pg.120]

The UV-Vis spectrum of a solution of I2 and hexamethylbenzene in hexane exhibits absorptions at 368 and 515 nm. Assign these absorptions to electronic transitions, and explain how each transition arises. [Pg.559]

Absorption of light in the UV-visible part of the electromagnetic radiation spectrum is very sensitive to the oxidation state of conducting polymers. Light absorption causes electronic transition between the valence and conduction bands and the specific absorption peaks in the UV-visible spectrum are indicative of the nature of the charge carriers and the number of charge carriers present. [Pg.51]

One group has successfiilly obtained infonnation about potential energy surfaces without measuring REPs. Instead, easily measured second derivative absorption profiles are obtained and linked to the fiill RRS spectrum taken at a single incident frequency. In this way, the painstaking task of measuring a REP is replaced by carefiilly recording the second derivative of the electronic absorption spectrum of the resonant transition [, 59],... [Pg.1201]

Pump-probe absorption experiments on the femtosecond time scale generally fall into two effective types, depending on the duration and spectral width of the pump pulse. If tlie pump spectrum is significantly narrower in width than the electronic absorption line shape, transient hole-burning spectroscopy [101. 102. 103. 104. 105. 106. 107. 108. 109. 110. 111. 112 and 113] can be perfomied. The second type of experiment, dynamic absorption spectroscopy [57, 114. 115. 116. 117. 118. 119. 120. 121 and 122], can be perfomied if the pump and probe pulses are short compared to tlie period of the vibrational modes that are coupled to the electronic transition. [Pg.1979]

Electronic transitions in molecules in supersonic jets may be investigated by intersecting the jet with a tunable dye laser in the region of molecular flow and observing the total fluorescence intensity. As the laser is tuned across the absorption band system a fluorescence excitation spectrum results which strongly resembles the absorption spectrum. The spectrum... [Pg.396]

RAIRS spectra contain absorption band structures related to electronic transitions and vibrations of the bulk, the surface, or adsorbed molecules. In reflectance spectroscopy the ahsorhance is usually determined hy calculating -log(Rs/Ro), where Rs represents the reflectance from the adsorhate-covered substrate and Rq is the reflectance from the bare substrate. For thin films with strong dipole oscillators, the Berre-man effect, which can lead to an additional feature in the reflectance spectrum, must also be considered (Sect. 4.9 Ellipsometry). The frequencies, intensities, full widths at half maximum, and band line-shapes in the absorption spectrum yield information about adsorption states, chemical environment, ordering effects, and vibrational coupling. [Pg.251]

The preceding empirical measures have taken chemical reactions as model processes. Now we consider a different class of model process, namely, a transition from one energy level to another within a molecule. The various forms of spectroscopy allow us to observe these transitions thus, electronic transitions give rise to ultraviolet—visible absorption spectra and fluorescence spectra. Because of solute-solvent interactions, the electronic energy levels of a solute are influenced by the solvent in which it is dissolved therefore, the absorption and fluorescence spectra contain information about the solute-solvent interactions. A change in electronic absorption spectrum caused by a change in the solvent is called solvatochromism. [Pg.435]

The aforementioned conditions make an analysis of the effect of substituents in thiophene on the UV spectrum more difficult than in the benzene series. In benzene there are two widely separated areas of absorption with different intensities. In thiophene there are instead two or three absorption bands due to electronic transitions which overlap and are of similar intensity. Finally, two very low-intensity bands at 313 and 318 mja have been found in thiophene. ... [Pg.14]

The PL spectrum and onset of the absorption spectrum of poly(2,5-dioctyloxy-para-phenylene vinylene) (DOO-PPV) are shown in Figure 7-8b. The PL spectrum exhibits several phonon replica at 1.8, 1.98, and 2.15 eV. The PL spectrum is not corrected for the system spectral response or self-absorption. These corrections would affect the relative intensities of the peaks, but not their positions. The highest energy peak is taken as the zero-phonon (0-0) transition and the two lower peaks correspond to one- and two-phonon transitions (1-0 and 2-0, respectively). The 2-0 transition is significantly broader than the 0-0 transition. This could be explained by the existence of several unresolved phonon modes which couple to electronic transitions. In this section we concentrate on films and dilute solutions of DOO-PPV, though similar measurements have been carried out on MEH-PPV [23]. Fresh DOO-PPV thin films were cast from chloroform solutions of 5% molar concentration onto quartz substrates the films were kept under constant vacuum. [Pg.115]

For long (infinite) /am.v-polyacclylene chains, the treatment of quantum lattice fluctuations is very complicated, because many lattice degrees of freedom couple in a non-linear way to the lowest electronic transitions. We have recently shown that for chains of up to 70 CH units, the amount of relevant lattice degrees of freedom reduces to only one or two, which makes it possible to calculate the low-energy part of the absorption spectrum in an essentially exact way [681. It remains a challenge to study models in which both disorder and the lattice quantum dynamics are considered. [Pg.370]

The energy of electronic transitions corresponds to light in the visible, UV, and far-UV regions of the spectrum (Fig. 7.1). Absorption positions are normally expressed in wavelength units, usually nanometers (nm). If a compound absorbs in... [Pg.306]

Below 250 °C the spectrum of saturated sulfur vapor consists of unresolved absorption bands at 210, 265, and 285 nm caused by the electronic transitions of cyclo-Ss [11]. These bands have also been observed for Sg solutions in organic solvents and for thin films of sohd Sg (see below). [Pg.34]

In an earlier work, we have proposed a theoretical procedure for the spectroscopy of antiferromagnetically (AF) coupled transition-metal dimers and have successfully applied this approach to the electronic absorption spectrum of model 2-Fe ferredoxin. In this work we apply this same procedure to the [Fe2in - 82) P o - CeH48)2)2 complex in order to better understand the electronic structure of this compound. As in our previous work" we base our analysis on the Intermediate Neglect of the Differential Overlap model parameterized for spectroscopy (INDO/S), utilizing a procedure outlined in detail in Reference 4. [Pg.358]

Figure 4. The calculated spectrum of the complex after a Lorentzian band convolution. Region I is dominated by bridging-sulfur-to-iron CT transitions, while region II is mostly due to organic-sulfur-to-iron electron transitions. Regions I and II are explained in a MO diagram. The vertical lines correspond to the experimental bands observed in the absorption spectrum of the [Fe2 (J. - S2) P o - CqH4S) ) ] complex, from Reference 1. Figure 4. The calculated spectrum of the complex after a Lorentzian band convolution. Region I is dominated by bridging-sulfur-to-iron CT transitions, while region II is mostly due to organic-sulfur-to-iron electron transitions. Regions I and II are explained in a MO diagram. The vertical lines correspond to the experimental bands observed in the absorption spectrum of the [Fe2 (J. - S2) P o - CqH4S) ) ] complex, from Reference 1.

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See also in sourсe #XX -- [ Pg.232 ]




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