Homogeneous and heterogeneous triplet — triplet annihilation in anthracene-doped phenanthrene crystals

Delayed and prompt fluorescence spectra and delayed fluorescence decay data for 10^?5?10^?6 M/M crystals of anthracene in phenanthrene are reported. It is shown that these data indicate that a heterogeneous (host-dopant) annihilation process takes place which produces the excited singlet state of the host molecule.     

Dynamic nuclear polarization of proton spins via photoexcited triplet states: the system phenanthrene in fluorene

The proton spins in a single crystal of fluorene have been polarized by dynamic nuclear polarization via the photoexcited triplet state of phenanthrene guest molecules. It is possible to reach an enhancement of the proton polarization of 90 at 1.2 K where the thermal equilibrium polarization is 0.033%.     

Magnetic field effects on heterogeneous triplet—triplet annihilation in anthracene-doped phenanthrene

The orientation of an 8 kG magnetic field with respect to the crystallographic axes is shown to affect the intensity of anthracene delayed fluorescence in an anthracene-doped phenanthrene crystal. These results are consistent with the calculated locations of level-crossing resonances for anthracene trapped-phenanthrene triplet exciton heterofusion. The line shapes of these level crossing resonances appear to be rather different from those reported for other cases of heterofusion or homofusion magnetic field resonances.     

Time-resolved ESR study of the lowest excited triplet states of para-quinones in glassy matrices at 77 k

The lowest excited nπ* triplet of 9.10-anthraquinone, 1.4-naphthoquinone and 1,4-benzoquinone were studied in glassy matrices at 77 K using a time-resolved ESR method. The D value of the triplet state of 9,10-anthraquinone varied from ?0.351 cm^?1 in a polar solvent to ?0.318 cm^?1 in a non-polar solvent. Both 1,4-naphthoquinone and 1,4-benzoquinone in polar solvents showed triplet state spectra with a D value of ?0.330 cm^?1. A computer simulation revealed the existence of widely distributed zero-field splitting parameters in the glassy condition. These data are compared with an analysis of CIDEP results of para-quinones.     

Zero-field splittings in aromatic triplet states

The zero-field splitting parametersD andE have been calculated for naphthalene using T.B.M. and I. R. M. wave functions, and accurate values of all significant two, three and four centre dipolar interaction integrals. Agreement with experiment is improved in the case ofE, but is less satisfactory forD.     

Exciplexes in highly excited triplet states

A mechanism of energy transfer from highly excited triplet aromatic molecules has been developed, which involves a stage of formation of an exciplex between a highly excited energy-donor molecule and an unexcited energy-acceptor molecule. Interpretation of the experimental data on the shape and the intensity of triplet-triplet absorption bands and the energy transfer probability is presented. In this interpretation, the results of quantum-chemical calculations of the energies of highly excited triplet states of toluene and benzene molecules are used.     

Photodissociation of N2O: triplet states and triplet channel

The role of triplet states in the UV photodissociation of N(2)O is investigated by means of quantum mechanical wave packet calculations. Global potential energy surfaces are calculated for the lowest two (3)A' and the lowest two (3)A' states at the multi-reference configuration interaction level of electronic structure theory using the augmented valence quadruple zeta atomic basis set. Because of extremely small transition dipole moments with the ground electronic state, excitation of the triplet states has only a marginal effect on the far red tail of the absorption cross section. The calculations do not show any hint of an increased absorption around 280 nm as claimed by early experimental studies. The peak observed in several electron energy loss spectra at 5.4 eV is unambiguously attributed to the lowest triplet state 1(3)A'. Excitation of the 2(1)A' state and subsequent transition to the repulsive branch of the 2(3)A' state at intermediate NN-O separations, promoted by spin-orbit coupling, is identified as the main pathway to the N(2)((1)Σ(g)(+))+O((3)P) triplet channel. The yield, determined in two-state wave packet calculations employing calculated spin-orbit matrix elements, is 0.002 as compared to 0.005 ± 0.002 measured by Nishida et al. [J. Phys. Chem. A 108, 2451 (2004)].     

Static luminescence quenching by oxygen and nitric oxide for phenanthrene in glassy matrices

Steady-state and pulsed methods have been applied to static phosphorescence and fluorescence quenching for phenanthrene caused by oxygen and nitric oxide. The characteristic fluorescence quenching distances have been determined for oxygen (8.7±0.5 Å) and nitric oxide (8.9±0,5 Å); the phosphorescence quenching involves an exchange mechanism, and measurements have been made on the characteristic quenching distances R₀ and exchange-interaction attenuation parameters L. Estimates have been made on the rate constants for dynamic quenching of the triplet excited states of phenanthrene in low-viscosity liquids, which agree well with the measured values for hexane.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 24, No. 6, pp. 667–672, November–December, 1988.     

Semiempirical calculations on triplet and doublet states

Restricted open-shell SCF calculations are carried out on triplet states of electron systems and doublet states of some of their ions. The results are compared with the ones obtained by limited configuration interaction and by the use of Koopman's theorem. For some examples open-shell SCF wavefunctions are expanded into linear combinations of Slater determinants representing configurations built from closed-shell SCF orbitals. This allows a more detailed comparison of the different methods of calculation.

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Zusammenfassung Berechnungen nach der beschränkten SCF Methode für offene Schalen werden an Triplettzuständen von -Elektronensystemen und Dublettzuständen einiger ihrer Ionen ausgeführt. Die Resultate werden mit denjenigen verglichen, welche die beschränkte Konfigurationswechselwirkung und der Satz von Koopmans liefern. Die SCF Wellenfunktionen für offene Schalen werden, für gewisse Beispiele, in Linearkombinationen von Slater-Determinanten entwickelt, welche aus SCF Orbitalen für geschlossene Schalen aufgebaut sind und verschiedene Konfigurationen darstellen. Dies erlaubt einen eingehenderen Vergleich der verschiedenen Berechnungsmethoden.

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Résumé Des calculs selon la méthode SCF avec restriction pour les couches ouvertes sont effectués sur les états triplets de systèmes d'électrons et sur les états doublets de certains de leurs ions. Les résultats sont comparés à ceux obtenus par la méthode d'interáction de configurations limitée et par l'emploi du théorème de Koopmans. Pour certains exemples les fonctions SCF à couches ouvertes sont développées en combinaison linéaire de déterminants de Slater représentant des configurations bâties à partir d'orbitales S.C.F. de couches fermées. Cela permet une comparaison plus détaillée des différentes méthodes de calcul.

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Presented in parts at the Theoretical Chemistry Symposium in Vienna, March 1967.     

“Fast” triplet excimer formation in fluid solutions of dinaphthylalkanes

In fluid solutions, α,α-dinaphthylalkanes from triplet excimers instantaneously with excitation by a nanosecond laser pulse (≈ 17 ns pulse width). The temporal characteristics and chain-length dependence of this “fast” triplet excimer formation suggest that the precursor of the excimer is a ground-state van der Waals dimer. These results are discussed in relation to possible conformational similarities between the triplet excimer and ground-state dimer, and conformation-enhanced spin-orbit coupling.     

Temperature dependence of the lifetime of pyrene triplet excimer emission

The stabilisation enthalpies of two different kinds of triplet excimers of pyrene are calculated from the temperature dependence of the triplet lifetime. They are found to be 800 cm⁻¹ and 2000 cm⁻¹.     

Plastic and glassy crystal states of caffeine

The present paper focuses on the high temperature form I of caffeine and on its low temperature metastable form. Structural, dynamic, and kinetic information has been obtained by X-ray, dielectric, and calorimetric investigations. This study shows the following features: (1) The high temperature phase (I) of caffeine is in a state of dynamically orientationally disordered crystalline state (so-called "plastic, or rotator, phase"). (2) This high-symmetry hexagonal phase can be maintained at low temperature in a metastable situation. (3) Under deep undercooling of form I a glass transition occurs in the disordered crystalline state near room temperature. It is associated with the orientational freezing in of the molecular motions. Otherwise stated, the metastable state I enters into a nonergodic unstable state, so-called "glassy crystal" state. These findings rationalize the difficulties seen with caffeine in pharmaceutical science.     

Lowest excited triplet states of hypericin and isohypericin

The fluorescence and phosphorescence of hypericin and isohypericin were studied in an ethanol matrix at 1.2 K. The prompt fluorescence spectra are mirror images of the absorption around the 0-0 transition, as expected. The 0-0 vibronic lines of the phosphorescence are found at 13190 and 13622 cm⁻¹, and the phosphorescence decay times are 2.79 and 6.6 ms at 1.2 K for hypericin and isohypericin respectively. The fluorescence excitation spectrum of isohypericin reveals a small trace of a different pigment, possibly a tautomeric form of isohypericin. The decay of the phosphorescence of isohypericin is biexponential. The slow component is attributed to an unknown contaminant with a high quantum yield of phosphorescence.     

Low-lying singlet and triplet electronic states of RhB

The low-lying XSigma+, a3Delta, A1Delta, b3Sigma+, B1Pi, c3Pi, C1Phi, D1Sigma+, E1Pi, d3Phi, and e3Pi electronic states of RhB have been investigated at the ab initio level, using the multistate multiconfigurational second-order perturbation (MS-CASPT2) theory, with extended atomic basis sets and inclusion of scalar relativistic effects. Among the eleven electronic states included in this work, only three (the X1Sigma+, D1Sigma+, and E1Pi states) have been investigated experimentally. Potential energy curves, spectroscopic constants, dipole moments, binding energies, and chemical bonding aspects are presented for all electronic states.     

Predissociation and autoionization of triplet Rydberg states in molecular hydrogen

We present single-photon spectroscopy in molecular hydrogen starting from the metastable c3Piu- state to a number of triplet nd-Rydberg states (v = 0 - 4, n = 12 - 20). Using fast beam spectroscopy both the autoionization channel and the predissociation channel are quantified, field free, as well as with small electric fields. Coupling with the i3Pig state is assumed to be responsible for field-free predissociation of the v = 0 Rydberg levels. The stronger observed predissociation channel of the v = 1 Rydberg levels is due to the nonadiabatic interaction with the h3Sigmag+ state in combination with l mixing due to an external electric field. No direct evidence is found for possible electric field induced predissociation of the gerade Rydberg states by low lying ungerade states. The competition between autoionization and predissociation is discussed in terms of possible consequences for dissociative recombination involving low energy electron collisions with the H2+ molecular ion.