Transition intensities dimers

Figure 44. Behavior of vibrational energies and infrared and Raman transition intensities as a function of Xj, under lowering of symmetry in the benzene dimer,...

It is also possible to measure microwave spectra of some more strongly bound Van der Waals complexes in a gas cell ratlier tlian a molecular beam. Indeed, tire first microwave studies on molecular clusters were of this type, on carboxylic acid dimers [jd]. The resolution tliat can be achieved is not as high as in a molecular beam, but bulk gas studies have tire advantage tliat vibrational satellites, due to pure rotational transitions in complexes witli intennolecular bending and stretching modes excited, can often be identified. The frequencies of tire vibrational satellites contain infonnation on how the vibrationally averaged stmcture changes in tire excited states, while their intensities allow tire vibrational frequencies to be estimated. 

As early as 1990, Chauvin and his co-workers from IFP published their first results on the biphasic, Ni-catalyzed dimerization of propene in ionic liquids of the [BMIM]Cl/AlCl3/AlEtCl2 type [4]. In the following years the nickel-catalyzed oligomerization of short-chain alkenes in chloroaluminate melts became one of the most intensively investigated applications of transition metal catalysts in ionic liquids to date. 

Firstly, we focus on cofacial dimers formed by stilbene molecules in such conformations, the amplitude of interchain interactions is expected to be maximized [57], Table 4-1 collects the INDO/SCl-calculated transition energies and intensities of the lowest two excited states of stilbene dimers for an interchain distance ranging from 30 to 3.5 A. 

Figure 4-11. INDQ/SCI-caleulalcd evolution of the transition energies (upper pan) and related intensities (bottom pan) of the lowest two optical transitions of a cofacial dimer formed by two stilbenc molecules separated by 4 A as a function of the dihedral angle between the long molecular axes, when rotating one molecule around the stacking axis and keeping the molecular planes parallel (case IV of Figure 4-10). Open squares (dosed circles) correspond to the S(J - S2 (S0 — S, > transition.

Figure 4-5. lNDO/SCl-calculalcd transition energies of the lowest two optical transitions of a cofacial dimer formed by two slilhcnc molecules as a function of interchain distance. The horizontal line refers to the transition energy of the isolated molecule. Note that the upper value reported at 3.S A corresponds to the transition to the fifth excited stale, which provides the lowest intense absoiption feature. 

As a prelude to our binding studies, the secondary structure of aPNA itself was examined using CD spectroscopy [52]. The first aPNA to be studied was the tail-to-tail bl dimer, [Ac-Cys-Gly-Ser -Asp-Ala-Glu-Ser -Ala-Ala-Lys-Ser -Ala-Ala-Glu-Ser -Ala-Aib-Ala-Ser -Lys-Gly-NH2]2- The far-UV CD spectra of this aPNA in water at 30 °C showed the double minimum at 220 nm (n-n transition) and 206 nm (n-n transition) as well as the maximum at 193 nm (n-n transition), characteristic of a peptide a-hehx. Upon increasing the temperature, the intensity of the minimum at 200 nm decreased indicating a transition from a-helix to random stracture. An isodichroic point at 202 nm was suggestive of a temperature-depen-dent a-helix to random coil transition. The helical content of this T5(bl)-dimer at 20°C in water was estimated to be 26% [40]. 

Organic Molecules It can be seen from our earlier discussion that the presence of a transition metal ion is not always required for an electrochromic effect. Indeed, many organic molecules can yield colored products as a result of reversible reduction or oxidation. 4,4 -Bipyridinium salts are the best known example of such compounds. These compounds can be prepared, stored, and purchased in colorless dicationic form (bipm +). One electron reduction of the dication leads to the intensely colored radical cation (bipm+ ). Such radical cations exist in equilibrium with their dimers (bipm ). In the case of methyl viologen, the radical cation is blue and the dimer is red. By varying the substient group in the molecule, different colors can be obtained. 

The electronic absorption and emission spectra and emission lifetimes of [Ir(/x-L)(CO)2]2 (L = pz, mpz and dmpz) have been determined.529 The intense low-energy absorption band around 400 nm is assigned to a d/2 > pz electronic transition. The three complexes all emit around 740 nm at 300 K and 670 nm at 77 K. The dimer excited states are stabilized relative to monomer levels by strong metal-metal bonding. 

The X-ray diffraction crystal structure of another copper dimer showed a distance between ligand planes of 2.91 to 3.31 A, an intramolecular Cu-Cu distance of 6.01 A and an intermolecular Cu-Cu distance of 10.209 A.32 Calculation of the Cu-Cu distance based on the relative intensity of the half-field transition gave r = 5.88 A. 

For the dimer (18), at 200 K, the ESR powder spectrum shows an intense central signal and a strong half-field absorption.427 Below 200 K, well-resolved hyperfine structure appears. The hyperfine constant for the half-field transition, 84 G, is approximately half of the Az value for the monomers. From single crystal ESR,427 the exchange integral -410 cm"1,... 

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