Vibronic structures

Reverting to the vibronic structure, the operator j again commutes with H, and the analogue of the lower adiabatic eigenstate of j in Eq. (66) becomes... 

The situation in singlet A electronic states of triatomic molecules with linear equilibrium geometry is presented in Figme 2. This vibronic structure can be interpreted in a completely analogous way as above for n species. Note that in A electronic states there is a single unique level for K =, but for each other K 0 series there are two levels with a unique character. 

The vibronic structure of a electronic state at variable strengths of the vibronic and spin-orbit coupling is presented in Figure 5. The splitting of the... 

Figure 11. Left Vibronic structure of the X Tl state of HCCS derived by Tang and Saito from experimental findings (Fig. 3 of [139]). Right Corresponding results of the ab initio study presented in [152].

Schmidtke H-H, Degan J (1989) A Dynamic Ligand Field Theory for Vibronic Structures Rationalizing Electronic Spectra of Transition Metal Complex Compounds. 71 99-124 Schneider W (1975) Kinetics and Mechanism of Metalloporphyrin Formation. 23 123-166... 

Further examples of emissive cyclometallated gold(III) complexes are [Au(L)Cl] (L = tridentate carbanion of 4 -(4-methoxyphenyl)-6 -phenyl-2,2 -bipyridine) [53], as well as mono- and binuclear bis-cyclometallated gold(III) complexes, namely [Au (C N C )L ]" (C N C = tridentate dicarbanion of 2,6-diphenylpyridine L = depro-tonated 2-mercaptopyridine (2-pyS ), n = 0 L = PPh3 or 1-methylimidazole, n = 1) and [Au2(C N C )2(P P)](C104)2 (P P = dppm, dppe) respectively [54]. The crystal structures of the binuclear derivatives show intramolecular interplanar separations of 3.4 A between the [Au(C N C)] moieties, implying the presence of weak n-n interactions. The mononuclear complexes show absorption with vibronic structure at 380-405 nm (e > 10 cm ), attributed to metal-perturbed intraligand transition. 

The gold(III) complexes, ]Au(C N C)L ]" and [Au2(C N C)2(P P)[(C104)2 are emissive in acetonitrile at low temperature. The frozen-state (77 K) emission spectra of the mononuclear complexes [Au(C N C )L [" show well-resolved vibronic structures with spacings in the 1100-1300 cm range, which correlate with the skeletal vibrational frequency of the tridentate C N C ligand. By comparing the emission... 

Emission spectra at these points are shown in Figure 8.2d. The band shapes were independent of the excitation intensity from 0.1 to 2.0 nJ pulse . The spectrum of the anthracene crystal with vibronic structures is ascribed to the fluorescence originating from the free exdton in the crystalline phase [1, 2], while the broad emission spectra of the pyrene microcrystal centered at 470 nm and that of the perylene microcrystal centered at 605 nm are, respectively, ascribed to the self-trapped exciton in the crystalline phase of pyrene and that of the a-type perylene crystal. These spectra clearly show that the femtosecond NIR pulse can produce excited singlet states in these microcrystals. 

Pelletier and Reber315 present new luminescence and low-energy excitation spectra of Pd(SCN)42 in three different crystalline environments, K2Pd(SCN)4, [K(18-crown-6)]2Pd(SCN)4, and (2-diethylammonium A -(2,6-dimethylphcnyl)acetamide)2Pd(SCN)4, and analyze the vibronic structure of the luminescence spectra, their intensities, and lifetimes as a function of temperature. The spectroscopic results are compared to the HOMO and LUMO orbitals obtained from density functional calculations to qualitatively illustrate the importance of the bending modes in the vibronic structure of the luminescence spectra. 

Because of our obvious prejudices we will describe this study in some detail. The energy levels of the acetophenone and -methylstyrene moieties are ideally situated for intramolecular triplet energy transfer (see Figure 6.12). If these two chromophores are not interacting, then the absorption spectra for these compounds should be the composite of the acetophenone-/ -methylstyrene spectra. Figure 6.13 indicates that this is true for n = 4 (and also 2 and 3) however, it is not correct for n = 1 (Figure 6.14). In the case of n = 1 the increased intensity of the vibronic structure of the n - n ... 

Exciplexes are complexes of the excited fluorophore molecule (which can be electron donor or acceptor) with the solvent molecule. Like many bimolecular processes, the formation of excimers and exciplexes are diffusion controlled processes. The fluorescence of these complexes is detected at relatively high concentrations of excited species, so a sufficient number of contacts should occur during the excited state lifetime and, hence, the characteristics of the dual emission depend strongly on the temperature and viscosity of solvents. A well-known example of exciplex is an excited state complex of anthracene and /V,/V-diethylaniline resulting from the transfer of an electron from an amine molecule to an excited anthracene. Molecules of anthracene in toluene fluoresce at 400 nm with contour having vibronic structure. An addition to the same solution of diethylaniline reveals quenching of anthracene accompanied by appearance of a broad, structureless fluorescence band of the exciplex near 500 nm (Fig. 2 )... 

It should be noted that the calculated anisotropy may not be applied to fs time-resolved anisotropy measurements because fs time-resolved experiments involve pumping and probing conditions and may involve overlapping between the vibronic structures of several electronic states due to the use of fs laser pulses. Nevertheless, we think the calculated anisotropy using Eq. (2.54) can provide a reference in comparing models. 

Reverting to the vibronic structure, the operator j again commutes with H,... 

The magnitudes of geometric changes in molecules on electronic excitation can be determined from the excitation profiles of resonance-enhanced Raman bands, most accurately where both the resonant absorption band and the profiles show vibronic structure. 

Some results are given in Figure 1 for [MnC ]", and related ones have been obtained for [ReS ]", [MoS ]2" and [WS ]2" (J -7), for each of which the lowest electric-dipole-allowed transition (1t2 Uj) is clearly vibronically structured (a situation which is brought about by the fact that ouj > r). The best fit 6 value derived for each ion (0.05-0.09 %) indicates that, in the T2 state, the change undergone is rather larger than that typical of a one-electron reduction of the ion e.g. 0.03 A for [MnO (8). 

Unfortunately, the above analysis can never be widely applicable to the determination of excited-state geometries since so few molecules and ions exhibit vibronically structured absorption bands and excitation profiles, even at low temperatures. Moreover, some questions arise as to the possible breakdown of the Condon approximation. Other types of molecule for which similar analyses have been carried out include 3-carotene, carotenoids (9) and certain carotenoproteins such as ovorubin (10). In these cases the excitation profiles of three skeletal a bands are monitored, and estimates for the change in C-C and C=C bonds lengths ( 0.02 A) have been made. 

As a final note on the general character of electronic IET spectra, we point out that vibronic structuring of electronic LETS has been known in M-I-A-M structures for many years [55, 74], In recent times, it has also been demonstrated in the STM environment [81]. 

Keywords Spin crossover Ligand field theory Optical properties Vibronic structure Configurational coordinate... 

---