Electronic transitions/spectra

With the advent of state-of-the-art hardware and advanced algorithms, quantum chemical methods are now routinely used to study groimd state properties of nucleic acid bases and related molecules at a high level of accuracy. " However, such a level of affordability is still far away for excited state calculations. Certain ab initio calculations of electronic spectra, transition moments and excited state geometries of nucleic acid bases and related molecules are reported. However, excited state studies are far less in numbers than those dealing with the ground state properties of nucleic acid bases. 

Detection of hydrogen is a particularly important problem for astrochemists because to a first approximation all visible matter is hydrogen. The hydrogen molecule is the most abundant molecule in the Universe but it presents considerable detection problems due to its structure and hence spectroscopy. Hydrogen does not possess a permanent dipole moment and so there is no allowed rotation or vibration spectrum and all electronic spectrum transitions are in the UV and blocked by the atmosphere. The launch of the far-UV telescope will allow the detection of H2 directly but up to now its concentration has been inferred from other measurements. The problem of detecting the H atom, however, has been solved using a transition buried deep in the hyperflne structure of the atom. 

Callomom J H and Innes K K 1963 Magnetic dipole transition in the electronic spectrum of formaldehyde J. Mol. Spectrosc. 10 166-81... 

After you compute an electronic spectrum with HyperChcni, you can use the table below to assign computed transitions and qiiali-tatively assess the accuracy of the com putation ... 

When you consider the selection rules, which are not particularly restrictive (see Section 7.1.6), governing transitions between these states arising from each configuration, it is not surprising that the electronic spectrum of an atom such as zirconium consists of very many lines. (Remember that the Laporte rule of Equation (7.33) forbids transitions between states arising from the same configuration.)... 

Eg term. A magnetic moment of around 5.5 BM (i.e. 4.90 BM- -orbital contribution) is expected for pure octahedral symmetry but, in practice, distortions produce values in the range 5.2-5.4BM. Similarly, in the electronic spectrum, the expected single band due to the Eg t ge g) T2g t ge ) transition is broadened... 

In our opinion the spin-flip (SF) phetse transition occurring in AF Cr may be connected with the electron spectrum anisotropy. This transition, observed in... 

AF Cr at 118/f, manifests itself in the fact that the longitudinal polarization of the SDW changes to the transversal one. From the standpoint of electronic structure, the nature of such SF transition in chromium is still unclear. Moreover, this transition is unlikely to be explained within the framework of non relativistic treatment, the nonrelativistic electron spectrum being identical for the longitudinal and transversal SDW. 

Occasionally, some bands which might otherwise be expected to be weak are observed to be quite strong. Two examples are shown in Fig. 4-4. The first shows the electronic spectrum of a solution containing [CoC ] ions in nitromethane. For this cT system, we expect three spin-allowed transitions and these are observed at roughly 3500, 7000 and 14,000 cm h They correspond (see Chapter 3) to the excitations M2 —> Ti F) and T P) respectively. Note, however, that the... 

Stable Mn(HI) compounds, Mn(R2r fc)3, have been known for a long time (42, 46). The structure of Mn(Et2C tc)3 is elucidated (47). The inner geometry of the Mn(CS2)3 core does not conform to the usual D3 point symmetry of transition metal complexes of this type, but shows a strong distortion attributed to the Jahn-Teller effect. The electronic spectrum (48, 49) and the magnetic properties of this type of complexes are well studied (50). 

Several types of spin-lattice relaxation processes have been described in the literature [31]. Here a brief overview of some of the most important ones is given. The simplest spin-lattice process is the direct process in which a spin transition is accompanied by the creation or annihilation of a single phonon such that the electronic spin transition energy, A, is exchanged by the phonon energy, hcoq. Using the Debye model for the phonon spectrum, one finds for k T A that... 

However, the significant changes in the electronic spectrum of PDHS at the transition temperature suggest that the nature of the backbone chromophore is also being altered during the process. 

Evaluation of the Work Term from Charge Transfer Spectral Data. The intermolecular interaction leading to the precursor complex in Scheme IV is reminiscent of the electron donor-acceptor or EDA complexes formed between electron donors and acceptors (21). The latter is characterized by the presence of a new absorption band in the electronic spectrum. According to the Mulliken charge transfer (CT) theory for weak EDA complexes, the absorption maximum hv rp corresponds to the vertical (Franck-Condon) transition from the neutral ground state to the polar excited state (22). 

The electronic spectrum of the complex consists of a combination of the spectra of the parent compounds plus one or more higher wavelength transitions, responsible for the colour. Charge transfer is promoted by a low ionization energy of the donor and high electron affinity of the acceptor. A potential barrier to charge transfer of Va = Id — Ea is predicted. The width of the barrier is related to the intermolecular distance. Since the same colour develops in the crystal and in solution a single donor-acceptor pair should be adequate to model the interaction. A simple potential box with the shape... 

In ideal situations, optical spectroscopy as a function of temperature for single crystals is employed to obtain the electronic spectrum of a SCO compound. Knowledge of positions and intensities of optical transitions is desirable and sometimes essential for LIESST experiments, particularly if optical measurements are applied to obtain relaxation kinetics (see Chap. 17). In many instances, however, it has been demonstrated that measurement of optical reflectivity suffices to study photo-excitation and relaxation of LIESST states in polycrystalline SCO compounds (cf. Chap. 18). 

I consider there to be a sharp distinction between the most polar form of a molecule and its ionically dissociated form. The reason for this is empirical An ion is defined as a species carrying a charge equal to an integral multiple of the electronic charge, and this definition implies that it will have a characteristic predictable electronic spectrum and, under suitable conditions, mobility in an electric field. There is so far no evidence which would compel one to abandon this definition, and I think it is important to distinguish clearly in this context between reaction intermediates (chain carriers, active species) of finite life-time, and transition states. 

Spectroscopic techniques such as electron spin resonance (ESR) offer the possibility to "probe" the chemical environment of the interlayer regions. With the ESR technique, an appropriate paramagnetic ion or molecule is allowed to penetrate the interlayer, and chemical information is deduced from the ESR spectrum. Transition metal ions, such as Cu2+, and nitroxide radical cations, such as TEMPAMINE (4-amino-2,2,6,6-tetramethylpiperidine N-oxide) have been used as probes in this manner (6-14). Since ESR is a sensitive and non-destructive method, investigations of small quantities of cations on layer silicate clays at various stages... 

The ligand (2) is soluble in DMSO. The UV-vis spectra of the hgand and Cu(I) complex were recorded in methanol. In the electronic spectrum a band appears at 283 mn which can be assigned to the ti-ti transition of C = C, C = N group in the ligand. The electronic spectra of the complex are showed 290 mn. 

The resonance Raman enhancement profiles In Figures 7 and 8 show that the maximum Intensity of the Fe-O-Fe symmetric stretch falls to correspond to a distinct absorption maximum In the electronic spectrum. This Implies that the 0x0 Fe CT transitions responsible for resonance enhancement are obscured underneath other, more Intense bands. Although strong absorption bands In the 300-400 nm region (e > 6,000 M" cm"l) are a ubiquitous feature of Fe-O-Fe clusters, the Raman results make It unlikely that they are due to 0x0 -> Fe CT. An alternative possibility Is that they represent simultaneous pair excitations of LF transitions In both of the... 

---