Molecules absorption spectra

Values of e span a very wide range, from near 0 to nearly 106. The former are characteristic of forbidden transitions such as singlet-triplet absorptions which are spin-forbidden the latter can be found in the absorption spectra of some dyes which have very strong colour in dilute solutions. Since values of e can vary between 0 and 106 for certain molecules, absorption spectra are often given on a logarithmic scale. 

In order to investigate the interaction between poly(DBF) and the acceptor molecule, absorption spectra were taken in a chloroform solution and in film (Fig. 28). Both in the solution and in the film, a weak band, probably due to donor-acceptor interaction, appeared around 520 nm in the mixture of poly(DBF) and TNFMN in addition to the bands due to poly(DBF) and TNFMN. These results indicate that TNFMN is an effective electron accepting dopant toward poly(DBF). In addition, the spectra indicate that pure poly(DBF) absorbs much less than TNFNM and the mixture at 337 nm. This means that N2 laser irradiation in TOF experiments will mainly excite the acceptor band or the donor-acceptor band to induce charge separation. 

Nakashima, K., K. Uchida-Kai, M. Koyanogi, and Y. Kanda (1982), Solvent effects on the intensities of forbidden bands of molecules. Absorption spectra of acetone and cyclopentanone. Bull Chem. Soc. Japan, 55, 415-419. 

Figure A3.12.8. Possible absorption spectrum for a molecule which dissociates via isolated compound-state resonances. Eq is the unimolecular threshold. (Adapted from [4].)...

While a laser beam can be used for traditional absorption spectroscopy by measuring / and 7q, the strength of laser spectroscopy lies in more specialized experiments which often do not lend themselves to such measurements. Other techniques are connnonly used to detect the absorption of light from the laser beam. A coimnon one is to observe fluorescence excited by the laser. The total fluorescence produced is nonnally proportional to the amount of light absorbed. It can be used as a measurement of concentration to detect species present in extremely small amounts. Or a measurement of the fluorescence intensity as the laser frequency is scaimed can give an absorption spectrum. This may allow much higher resolution than is easily obtained with a traditional absorption spectrometer. In other experiments the fluorescence may be dispersed and its spectrum detennined with a traditional spectrometer. In suitable cases this could be the emission from a single electronic-vibrational-rotational level of a molecule and the experimenter can study how the spectrum varies with level. 

Fragnito H L, Bigot J-Y, Becker P C and Shank C V 1989 Evolution of the vibronic absorption spectrum in a molecule following impulsive excitation with a 6 fs optical pulse Chem. Phys. Lett. 160 101 ... 

To verify effectiveness of NDCPA we carried out the calculations of absorption spectra for a system of excitons locally and linearly coupled to Einstein phonons at zero temperature in cubic crystal with one molecule per unit cell (probably the simplest model of exciton-phonon system of organic crystals). Absorption spectrum is defined as an imaginary part of one-exciton Green s function taken at zero value of exciton momentum vector... 

Information about the structure of a molecule can frequently be obtained from observations of its absorption spectrum. The positions of the absorption bands due to any molecule depend upon its atomic and electronic configuration. To a first approximation, the internal energy E oi a, molecule can be regarded as composed of additive contributions from the electronic motions within the molecule (Et), the vibrational motions of the constituent atoms relative to one another E ), and the rotational motion of the molecule as a whole (Ef) ... 

The above figure shows part of the infrared absorption spectrum of HCN gas. The molecule has a CH stretching vibration, a bending vibration, and a CN stretching vibration. 

At first, the dimeric nature of the base isolated from 3-ethyl-2-methyl-4-phenylthiazolium was postulated via a chemical route. Indeed the adduct of ICH, on a similar 2-ethylidene base is a 2-isopropylthiazolium salt in the case of methylene base it is an anilinovinyl compound identified by its absorption spectrum and chemical reactivity (45-47). This dimeric structure of the molecule has been definitively established by its NMR spectrum. It is very similar to the base issued from 2.3-dimethyl-benzo thiazolium (48). It corresponds to 2-(3 -ethyl-4 -phenyl-2 -methylenethiazolinilydene)2-methyl-3-ethyl-4-phenylthiazoline (13). There is only one methyl signal (62 = 2.59), and two series of signals (63= 1.36-3.90, 63= 1.12-3.78) correspond to ethyl groups. Three protons attributed to positions T,5,5 are shifted to a lower field 5.93, 6.58, and 8.36 ppm. The bulk of the ten phenyl protons is at 7.3 ppm (Scheme 22). 

Due to the structure of the symmetrical anhydrobase. every time a 2-methylthiazolium undergoes the attack of a base, theoretically it can result in two trimethine thiazolocyanines the mesomethylsubstituted one and the unsubstituted one. For an unexplained reason, it seems that when position 5 of the starting molecule is substituted, only the mesomethyl dye is produced according to the absorption spectrum, 530 nm for the methylmeso and 569 nm for the 4-phenyl substituted derivative (Scheme 29). ... 

In a MALDl experiment, the sample is mixed or dissolved in a matrix material that has an absorption spectrum matching the laser wavelength of energy, The sample may not have a matching absorption peak (a), but this is not important because the matrix material absorbs the radiation, some of which is passed on to the dissolved sample. Neutral molecules and ions from both sample and matrix material are desorbed (b). 

Figure 5.12 shows the J= — 0 transition of the linear molecule cyanodiacetylene (H—C=C—C=C—C=N) observed in emission in Sagittarius B2 (Figure 5.4 shows part of the absorption spectrum in the laboratory). The three hyperfine components into which the transition is split are due to interaction between the rotational angular momentum and the nuclear spin of the nucleus for which 1= 1 (see Table 1.3). The vertical scale is a measure of the change of the temperature of the antenna due to the received signal. 

Because of the relatively high population of the u" = 0 level the v" = 0 progression is likely to be prominent in the absorption spectrum. In emission the relative populations of the i/ levels depend on the method of excitation. In a low-pressure discharge, in which there are not many collisions to provide a channel for vibrational deactivation, the populations may be somewhat random. However, higher pressure may result in most of the molecules being in the v = 0 state and the v = 0 progression being prominent. 

Figure 9.18 shows a typical energy level diagram of a dye molecule including the lowest electronic states Sq, and S2 in the singlet manifold and and T2 in the triplet manifold. Associated with each of these states are vibrational and rotational sub-levels broadened to such an extent in the liquid that they form a continuum. As a result the absorption spectrum, such as that in Figure 9.17, is typical of a liquid phase spectrum showing almost no structure within the band system. 

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... 

Molecules and atoms interact with photons of solar radiation under certain conditions to absorb photons of light of various wavelengths. Figure 10-4 shows the absorption spectrum of NO2 as a function of the wavelength of light from 240 to 500 nm. This molecule absorbs solar radiation from... 

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. 

Many other measures of solvent polarity have been developed. One of the most useful is based on shifts in the absorption spectrum of a reference dye. The positions of absorption bands are, in general, sensitive to solvent polarity because the electronic distribution, and therefore the polarity, of the excited state is different from that of the ground state. The shift in the absorption maximum reflects the effect of solvent on the energy gap between the ground-state and excited-state molecules. An empirical solvent polarity measure called y(30) is based on this concept. Some values of this measure for common solvents are given in Table 4.12 along with the dielectric constants for the solvents. It can be seen that there is a rather different order of polarity given by these two quantities. 

In Pedersen s early experiments, the relative binding of cations by crown ethers was assessed by extraction of alkali metal picrates into an organic phase. In these experiments, the crown ether served to draw into the organic phase a colored molecule which was ordinarily insoluble in this medium. An extension and elaboration of this notion has been developed by Dix and Vdgtle and Nakamura, Takagi, and Ueno In efforts by both of these groups, crown ether molecules were appended to chromophoric or colored residues. Ion-selective extraction and interaction with the crown and/or chromophore could produce changes in the absorption spectrum. Examples of molecules so constructed are illustrated below as 7 7 and 18 from refs. 32 and 131, respectively. 

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. 

As yet no quinazoline has been discovered which has any appreciable amount (say, 1%) of hydrated species in the neutral molecule,but several quinazolines were shown to contain a mixture of anhydrous and hydrated species in the cations. Anhydrous neutral molecules and anhydrous cations have an ultraviolet absorption spectrum of the general type C (Fig. 3) and hydrated cations, the type... 

When an ionic solution contains neutral molecules, their presence may be inferred from the osmotic and thermodynamic properties of the solution. In addition there are two important effects that disclose the presence of neutral molecules (1) in many cases the absorption spectrum for visible or ultraviolet light is different for a neutral molecule in solution and for the ions into which it dissociates (2) historically, it has been mainly the electrical conductivity of solutions that has been studied to elucidate the relation between weak and strong electrolytes. For each ionic solution the conductivity problem may be stated as follows in this solution is it true that at any moment every ion responds to the applied field as a free ion, or must we say that a certain fraction of the solute fails to respond to the field as free ions, either because it consists of neutral undissociated molecules, or for some other reason ... 

Absorption spectrum (Section 12.5) A plot of wavelength of incident light versus amount of light absorbed. Organic molecules show absorption spectra in both the infrared and the ultraviolet regions of the electromagnetic spectrum. 

Figure 16-36 shows the absorption spectra of thin films of four differently substituted five-ring OPVs. in contrast to the solution spectra, which show structureless low-energy absorption bands, the absorption bands of the films are structured. In the solid slate, the molecules are spatially constrained, whereas in solution different conformers exist, resulting in a distribution of accessible levels. As a consequence, some details appear in the absorption spectrum of the films which can be attributed to vibronic coupling, while, in dilute solution, the spectrum is a broad featureless band. For oct-OPV5 and Ooci-OPV5 films, the absorption maxima are red-shifted over approximately 0.1 eV relative to the solution (see Fig. 16-12). The low-energy absorption band of a thin film of Ooct-OPV5-CN" displays an appreciably larger...

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