The absorption spectra of the ferrate (VI) ion (FeO^2-₄) in K₂MO₄ (M = S, Se, Cr, Mo) host lattices consist of a series of relatively weak bands at low energy, which can be assigned to transitions within the partially filled 3d shell and some intense bands at higher energy, which are assigned to ligand-to-metal charge transfer transitions (LMCT). In the near-infrared (NIR) region sharp lines are observed belonging to the spin-forbidden spin-flip transitions ³A₂→ ¹E and ³A₂  → ¹A₁. The lowest excited state is the ¹E state, serving as initial state for ¹E → ³A₂ sharp-line luminescence at around 6200 cm^-1. Another luminescence is observed centered at 9000 cm^-1, which is assigned to the ³T₂ → ³A₂ transition. It is rather broad and three orders of magnitude weaker than the ¹E luminescence at 30K as a result of efficient non-radiative relaxation processes to the ¹E state. The temperature dependence of the total intensity and the lifetime of the ¹E → ³A₂ luminescence is understood within a complex scheme of radiative and non-radiative processes.

A spectroscopic study of supersonic jet‐cooled catechol (1,2‐dihydroxybenzene) and its d₁‐ and d₂‐isotopomers, deuterated at the hydroxy groups, was performed by resonant two‐photon ionization (R2PI) and fluorescence emission techniques, and supplemented by molecular‐beam hole‐burning experiments. The latter prove that one single rotamer of catechol is dominant under molecular beam conditions. The complicated vibrational structure in the S₀→S₁ spectrum from the 0⁰₀ band to 400 cm⁻¹ above is not due to three different rotamers, as previously thought, but is due to the excitation of a vibrational progression associated mainly with the torsion of the hydroxy groups. The torsional bands are very prominent in the R2PI spectra, but are weak in the emission spectra. Detailed analysis of the torsional bands was based on a fit to the S₁ and S₀ state frequencies and the Franck–Condon factors in absorption and emission, using a double‐minimum potential for the S₁ state and a harmonic potential for the S₀ state. In the S₁ state one of the two –O–H torsional mode frequencies is lowered from τ₂≊250 to ≊50 cm⁻¹, and the molecule is only quasiplanar with respect to the –O–H torsional coordinates.

Mass-selective ground state vibrational spectroscopy of the jet-cooled carbazole·Ar complex was performed by populating ground-state levels via a pump/dump laser pulse sequence, followed by selective resonant two-photon ionization of the vibrationally relaxed complexes. Intra- and inter-molecular van der Waals modes in the S₀ state are measurable with good signal/noise. The ground-state binding energy can be determined by detecting the negative signals resulting from loss of ground-state population via vibrational predissociation of the complex.

The cyclic water trimer shows a fascinating complexity of its intermolecular potential-energy surface as a function of the three intermolecular torsional coordinates: there are six isometric but permutationally distinct minimum-energy structures of C₁ symmetry, which can interconvert by torsional motions via six isometric transition states, also of C₁ symmetry. A second type of interconversion can occur through different torsional motions via two C₃ symmetric transition structures, and a third interconversion type via a planar C_3h symmetric transition structure. The equivalence of the six minima is broken if the ‘free’ H atom of one H₂O molecule in the cluster is chemically substituted, yielding three distinct conformers, which occur in enantiomeric pairs. Not all three conformers are necessarily locally stable minima; this depends on the substituent. The phenol–(H₂O)₂, p-cyanophenol–(H₂O)₂, 1-naphthol–(H₂O)₂ and 2-naphthol–(H₂O)₂ clusters, which are the phenyl, p-cyanophenyl and naphthyl derivatives of (H₂O)₃, were examined by resonant two-photon ionization spectroscopy in supersonic beams. These clusters exhibit S₀→ S₁ vibronic spectra with very different characteristics. These reflect the number of cluster structures formed, their low-frequency intermolecular vibrations and indirectly give information about the cluster fluxionality.

The mixed-metal ferromagnet {[P(Ph)4][MnCr(ox)3]}n, where Ph is phenyl and ox is oxalate, has been prepared and a two-dimensional network structure, extended by Mn(II)-ox-Cr(III) bridges, has been determined from single crystal X-ray data. Crystal data: space group R3c, a=b=18.783(3), c=57.283(24) Å, α=β=90, γ=120°, Z=24 (C30H20O12PCrMn). The magnetic susceptibility data obey the Curie-Weiss law in the temperature range 260–20 K with a positive Weiss constant of 10.5 K. The temperature dependence of the molar magnetization exhibits a magnetic phase transition at Tc=5.9 K. The structure is discussed in relation to the strategy for preparing molecular based ferromagnets and, in addition, it is a solution to the question of the dimensionality of the [MM'(ox)3]n network, which in principle can extend two- or three-dimensionally to the crystal lattice. The optical absorption spectra of the single crystals are assigned to the ‘CrO6' chromophores. Their polarization patterns reflect the electric dipole selection rules for D3 symmetry. A strong site selective luminescence from the chromium(III) 2E states is observed at low temperature and the system may be suitable for studying energy transfer mechanisms.

We have developed a model to describe the inhomogeneous broadening of optical spectra in the substitutionally disordered crystals. The comparison with the experimentalf–f fluorescence spectra of SrFCl_xBr_1−x:Sm²⁺ (0≤x≤1) allowed to establish, in a very detailed manner, the relationship between the inhomogeneous spectral distribution and the crystal structure around the Sm²⁺ impurity.

Single crystals of the alkaline earth fluorides doped with silver were grown successfully. This paper presents details of the methodology. The as-grown crystals consist of colorless transparent and yellowish regions. The former were shown to contain the Ag⁺ ion and the latter also silver pairs, small clusters and probably colloidal aggregates. Complex optical absorption bands were observed in the samples of the former parts after they had been X-irradiated. The samples were subsequently exposed to extended series of physico-chemical treatments with the aim to obtain information regarding the electronic structures involved. The evolution was monitored with the aid of optical absorption experiments. Factor analysis technique is presented and was applied to uncover mutually independent contributions to these absorption spectra. We identified the Jahn-Teller Ag⁺ [Bill H. et al., Solid State Commun.70, 511 (1989)] and several centers which formally involve an Ag⁻ ion.

The spectroscopic properties of Ag⁺-doped strontium fluoride crystals were investigated at various temperatures, using absorption and fluorescence spectroscopies. The system exhibits a strong ultraviolet emission upon excitation into the two principal absorption bands. The azimuthal dependence of the degree of polarization of this luminescence is analysed, as well as its dynamics. The monovalent silver ions are shown to substitute for a host cation, with cubic symmetry. This is the first reported example of a cubic coordination for the Ag⁺ ions in an insulator. This cubic field, together with the strong ionic character of the framework, confers rather original spectroscopic properties to this system. The luminescence mechanisms are interpreted on the basis of the measured decay times and with the aid of energy diagram calculations. Two closed thermalized spin-orbit levels, with symmetry A_2g and T_2g respectively, are involved in the luminescence processes. The pure spin triplet A_2g only emits at low temperatures (T<15 K), whereas the T_2g level ( approximately 2% spin singlet character) emits in turn upon warming the crystal. One-dimensional configuration coordinate diagrams are proposed to interpret the peculiar temperature dependence of the emission band maximum.

Transition metal chemistry contains a class of complex compounds for which the spin state of the central atom changes from high spin to low spin when the temperature is lowered. This is accompanied by changes of the magnetic and optical properties that make the thermally induced spin transition (also called spin crossover) easy to follow. The phenomenon is found in the solid state as well as in solution. Amongst this class, iron(II) spin crossover compounds are distinguished for their great variety of spin transition behavior; it can be anything from gradual to abrupt, stepwise, or with hysteresis effects. Many examples have been thoroughly studied by Mössbauer and optical spectroscopy, measurements of the magnetic susceptibilities and the heat capacities, as well as crystal structure analysis. Cooperative interactions between the complex molecules can be satisfactorily explained from changes in the elastic properties during the spin transition, that is, from changes in molecular structure and volume. Our investigations of iron(II) spin crossover compounds have shown that green light will switch the low spin state to the high spin state, which then can have a virtually unlimited lifetime at low temperatures (this phenomenom is termed light-induced excited spin state trapping - acronym: LIESST). Red light will switch the metastable high spin state back to the low spin state. We have elucidated the mechanism of the LIESST effect and studied the deactivation kinetics in detail. It is now well understood within the theoretical context of radiationless transitions. Applications of the LIESST effect in optical information technology can be envisaged.

In der Übergangsmetallchemie gibt es eine Klasse von Komplexverbindungen, bei denen eine Temperaturerniedrigung einen Wechsel im Spinzustand des Zentralatoms vom High-Spin- in den Low-Spin-Zustand bewirkt. Dabei ändern sich die magnetischen und optischen Eigenschaften, über die der thermische Spinübergang (auch Spincrossover genannt) sehr gut verfolgt werden kann. Dieses Phänomen tritt sowohl in flüssiger Phase als auch im Festkörper auf. Eine herausragende Stellung nehmen Eisen(II) - Spincrossover - Verbindungen ein, in denen der Spinübergang im Festkörper auf sehr unterschiedliche Weise - graduell, abrupt, mit Hysterese oder stufenweise - verlaufen kann und mit Mößbauer- und optischer Spektroskopie, mit magnetischen Suszeptibilitäts- und Wärmekapazitätsmessungen sowie durch Kristallstrukturanalyse intensiv untersucht worden ist. Die kooperative Wechselwirkung zwischen den einzelnen Komplexmolekülen kann befriedigend durch elastische Eigenschaften und durch die Änderung von Gestalt und Volumen der Komplexmoleküle beim Spinübergang erklärt werden. Bei Untersuchungen an Eisen(II)-Spincrossover-Verbindungen konnte man beobachten, daß sich der Low-Spin-Zustand mit grünem Licht in den High-Spin-Zustand umschalten läßt, der bei tiefen Temperaturen eine nahezu unendlich lange Lebensdauer haben kann (LIESST = Light-Induced Excited Spin State Trapping). Mit rotem Licht läßt sich der metastabile High-Spin- wieder in den Low-Spin-Zustand zurückschalten. Der Mechanismus des LIESST-Effekts ist aufgeklärt, die Zerfallskinetik im Detail untersucht und im Rahmen der Theorie strahlungsloser Übergänge verstanden. Anwendungen des LIESST-Effekts in der optischen Informationstechnik sind denkbar.

A study of the effect of an external electric field on spectral holes burnt at different frequencies in the inhomogeneous absorption band of a centrosymmetric squaraine dye, bis [4-(diethylamino)-2-hydroxyphenyl] squaraine (DEAH), in polymers of different polarity is presented. Average matrix induced dipole moment differences of about 1 D and 0.37 D were measured in the directions parallel and perpendicular to the long axis of DEAH. In all polymers investigated, the induced dipole moment difference decreased from the higher to the lower frequencies. Solvatochromic shift measurements were performed in order to elucidate the origin of this effect. The matrix field inducing the dipole moment is also partially responsible for the frequency shift of the absorption of DEAH. With increasing matrix field, the absorptiion frequency is shifted to the blue due to electrostatic interaction with the local dipoles of DEAH. The contribution of the electrostatic interactions to the frequency shift is smaller than the dispersion interactions by two orders of magnitude in polystyrene, but increases slightly in more polar polymers.

The free ion yield (R) resulting from the fluorescence quenching of 9,10-dicyanoanthracene (DCA) by various electron donors in acetonitrile has been studied using ns laser photoconductivity. The influence of the chemical nature of the doors is established in a general manner. For a given oxidation potential Eox(D/D+), the rate constant of geminate ion recombination, kbac, decreases significantly as the electronic delocalization of the donor increases. As a consequence multiple Marcus plots are observed in the inverted region. These plots show decreasing curvature when going from stilbenes to amines as donors. This fan effect is tentatively explained by considering the detailed roles of the parameters V, and h in the Marcus model.

The principles of ps transient grating spectroscopy are presented. The capabilities of this technique for the study of photoinduced processes are illustrated by several new results. These include the observation of an anomalous effect in the reorientation dynamics of two ionic dyes in long-chain alkanenitriles, the measurement of the local viscosity in the interior of reverse micelles containing methanol, and the determination of the rate constant of separation of a geminate radical pair formed by photoinduced electron-transfer reaction.

The rotational diffusion time of ruthenium (II)-bis(2,2'-bipyridine) (2,2'-biquinoleine) has been measured in polar solvents of different viscosity. The rotational dynamics can be explained in terms of the Stokes—Einstein—Debye hydrodynamics theory under stick boundary condition by considering the rotating body as a prolate spheroid enclosing the complex. This overestimates the intrinsic molecular volume by a factor of 1.5. The difference can be accounted for by solvent molecules intercalated in the interligand space and stabilized by electrostatic interaction with the charge of the metal atom.

The rate of separation into free ions of a geminate ion pair generated by photoinduced electron transfer between 9,lO-anthraquinone excited to the lowest triplet state and 1,2,4-trimethoxybenzenein 1,1,2,2-tetrachloroethane has been measured at different temperatures by nanosecond time-resolved resonance Raman spectroscopy (TR3). The intrinsic activation energy for the separation amounts to 0.04 eV, suggesting that the center-to-center interionic distance in the geminate ion pair is about 7.5 A. The activation barrier is due to a loss of electrostatic stabilization upon separation to a distance of about 9.5 A, where a solvent molecule or part of it can interpenetrate to increase the solvation energy. This suggests that the geminate ion pair is a loose ion pair but is not truly solvent separated.

The 3,6-substituted 1,2,4-trioxan-5-ones 11-14, on heating to 170-200°, underwent unimolecular thermolysis to generate electronically excited singlet ketones with an efficiency of ca. 0.2%. The chemiluminescence quantum yields (ΦoS_CL) depended on the nature of the 6-substitutents and increased linearly with temperature. The Arrhenius activation energies were obtained by measuring the rate of decay of luminescence and determined as 22.9, 30.4, 35.6, and 34.2 kcal/mol for 11-14, respectively. Step analysis of the chemiluminescence of 14 afforded an average activation energy of 44.3 kcal/mol. This latter result is explicable in terms of two decomposition paths, higher and lower in energy, leading to excited and 'dark' products, respectively. The thermolysis of trioxanones 12-14 lacking a H-atom at the 6-position is interpreted as involving successive rupture of the peroxide bond, excision of ketone at the 3-substituted end, and loss of CO₂, to finally produce ketone originating from the 6-position (see Scheme 4).