Intramolecular charge transfer state and unusual fluorescence from an upper excited singlet of a nonplanar derivative of p-cyano-N,N-dimethylaniline

The TICT (twisted internal charge transfer state) fluorescence of 4-cyano-2,6,N,N-tetramethylaniline (CTMA) was found in the vapour phase. The dipole moments of excited Franck-Condon and Franck-Condon twisted ground states were estimated from the solvent shifts of absorption and fluorescence. The near-equality of excited Franck-Condon and relaxed TICT state dipole moments is discussed. The fluorescence from an upper excited singlet state is found and its mechanism is explained.     

Structure of the excited biacetyl molecule and analysis of its absorption and fluorescence spectra

A structural-dynamical model of biacetyl and biacetyl-d ₆ molecules in the excited electronic state is derived on the basis of semiempirical correlations and the method of hybrid atomic orbitals. The vibrational structure of absorption and fluorescence spectra is calculated in satisfactory agreement with experimental data. Interpretation of the lines is corrected. The effect of variations in the molecule valence angles, caused by electronic excitation, on the intensity of vibrational components is ascertained. A possibility of calculating relatively small structural and spectral variations resulting from methyl substitution in the sequence of glyoxal, methylglyoxal, and biacetyl molecules is demonstrated.     

Gain and excited singlet and triplet state absorption spectra of some 9-acetoxy-10(halogenoacetoxy)phenylanthracenes

An apparatus for, optical gain spectra measurements is described, which has been used to determine the gain spectra of several halogen substituted derivatives of 9-acetoxy-10(2-acetoxy)phenylanthracenes. Using the determinedS ₁- andT ₁-excited state absorption spectra and other spectroscopic data the gain spectrum have been computed. The changes of the determined laser parameters and spectroscopic data of the halogen substituted derivatives are discussed with reference to the intramolecular heavy atom effect.Work partially supported within the project CPBP01.06 and from the Foreign Commission at the University of Bremen     

Fluorescence quenching in laser dyes by absorption from an excited singlet state

The effects of absorption of pump radiation from the first excited singlet state on the fluorescence quantum yield are calculated by numerical solution of simple rate equations, and compared with experiments performed earlier for the dye 7-diethylamino-4-methyl-coumarin at N₂-laser pumping. Analytical solutions for high and low pump intensities are found for the case of an optically thin solution.     

Lifetime of the second excited state of K

Energy distributions of neutrons from the (d, n) reactions on ^12–14C leading to unbound states of ^13–15N have been measured at 6.3 or 6.5 MeV deuteron energy. Angular distributions have been extracted for ^{13, 14}C(d, n) transitions and analysed with DWBA using the extra-polation technique to give l-values and transition strengths for ten unbound states in ¹⁴N and six in ¹⁵N. For the ¹⁵N level at 10.541 MeV it is concluded that J^π is $\text{3}\text{2}$^?. A new ¹⁵N level is observed at 11.44 MeV. The 0° (d, n) cross sections have been set in proportion to (p, p₀) resonance cross sections, and a pronounced l-dependence of the ratio is obtained.     

Time-resolved studies on the photoisomerization of a phenylene-silylene-vinylene type compound in its first singlet excited state

In femtosecond laser-flash photolysis experiments, the first singlet excited state of trans-ST, ((E,E)-{1,4-bis(2-dimethylphenylsilyl)ethenyl}benzene) showed a strong S1(π,π^?)-Sn absorption band at 540 nm in acetonitrile and at 550 nm in hexane. The lifetime of this state was determined to be 13.2±2.0 and 11.1±1.5 ps, respectively. Intersystem crossing was shown not to be a principal route for the deactivation of this S1 state of trans-ST. Evidence for this conclusion involved two complementary nanosecond laser-flash photolysis experiments. In one experiment involving direct excitation, no transient absorption spectrum was detected in the 350-650 nm spectral range. Yet, in the second experiment, on triplet sensitization, using xanthone, a transient absorption at 400 nm was tentatively assigned to the triplet state absorption of trans-ST. Photoisomerization was monitored in nanosecond time-resolved bleaching experiments. From these experiments the trans-cis photoisomerization quantum yield was determined to be 0.23 on direct trans-ST excitation. In a xanthone-sensitized stationary-state excitation experiment, the trans-cis isomerization quantum yield was determined to be 0.32. The main deactivation route of trans-ST in its S1 state is repopulation of the ground state directly through internal conversion or with the intermediacy of conformers with twisted geometry.     

Effectiveness of charge separation from the long-lived second excited state of donors

In molecular zinc-porphyrin-based donor–acceptor systems, the electron transfer from the second singlet excited state S₂ is accompanied by ultrafast recombination into the first excited state, resulting in a low quantum yield of the thermalized charge-separated state (20%). It is demonstrated that the quantum yield of ultrafast charge separation in donor–acceptor triads D–A₁–A₂ can be close to 100% in molecular systems with lifetimes of the S₂ state longer than 150 ps. As prototypes of such systems, donor–acceptor diads D–A₁ and triads D–A₁–A₂ are considered, wherein the xanthione molecule plays the role of a donor. The ranges of the model parameters are determined in which the efficiency of charge separation is high. The twostage photoinduced charge transfer is studied within the framework of a multichannel stochastic model that takes into account the reorganization of a polar solvent and a high-frequency intramolecular vibrational mode.     

Absorption,fluorescence, and fluorescence excitation spectra of free molecules of indole and its derivatives

We have obtained and analyzed the absorption, fluorescence, and fluorescence excitation spectra of indole vapor, N-acetyl-L-tryptophan vapor, and 3-indole aldehyde vapor. From analysis of the dependence of the fluorescence spectrum of the free indole molecules on the wavelength of the exciting radiation λ_ex, it follows that emission of fluorescence occurs when the molecules undergo a transition from the one electronically excited state ¹L_b. The fluorescence spectra of the studied compounds are insignificantly different, suggesting a major role for the indole chromophore in formation of the compounds. The absorption spectrum of N-acetyl-L-tryptophan, in which the group of atoms is added to the indole ring through a-C-C bond, is similar to the spectrum of indole, while the spectrum of 3-indole aldehyde is significantly different from the indole spectrum due to the effect of the C=O group conjugated with the indole ring. The fluorescence excitation spectra are considerably different from the absorption spectra. This is associated with the strong dependence of the quantum yield for the free molecules on λ_ex. Qualitatively, they are mirror-symmetric to the fluorescence spectra of the stodied compounds. Analysis of the data obtained provides a basis for assuming that in the case of free molecules of indole and its derivatives, the ¹L_a absorption in the extreme long-wavelength region of the spectrum does not overlap ¹L_b absorption. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 218–222, March–April, 2007.     

Lifetime of the second excited state in157Gd

The mean life of the 131.5 keV, 7/2^? state in¹⁵⁷Gd was measured using a modified version of the microwave method. The result obtained is \(\tau = 137 \pm 7ps.\) .The deduced magnetic parametersg _K, g_R are discussed and compared with theory.     

EPR spectra of the excited nitrogen state in 6H-SiC

A study is reported of donor EPR spectra in compensated 6H-SiC crystals with donor concentrations (N _D -N _A ) varied from 8×10¹⁷ to 5×10¹⁶ cm^?3, performed within a temperature interval from 77 to 170 K at a frequency of 37 GHz. A second paramagnetic state of nitrogen in silicon carbide has been found to exist, and it is associated with its excited 1S(E) state becoming paramagnetic after thermal ionization of the donor electrons from the 1S(A ₁) to 1S(E) level. The EPR spectrum of nitrogen in the 1S(E) state is a single line with an anisotropic width because of the unresolved hyperfine structure. A light-induced charge transfer between the ground, 1S(A ₁), and excited, 1S(E), nitrogen states has been observed. The valley-orbit splitting and the energy required to ionize donor electrons from the 1S(E) to higher lying excited states have been determined for the cubic nitrogen sites. The parameters of a structural defect, characteristic of n-type 6H-SiC compensated crystals, have been established.     

Soft dynamics of the excited state: Lambda-shaped optical spectra

Anomalous optical spectra of centres with strongly reduced local elastic constants in the excited electronic state are studied. In this case, transitions take place to the vicinity of a flat minimum of the potential energy in the configurational coordinate space. The existence of a flat minimum results in the appearance of the resonant (pseudo-local) mode of a low frequency. This leads to a strong enhancement of the low-frequency part of the phonon wing, causing a formation of the possibly modulated lambda-shaped optical spectra; the modulation comes from the Airy oscillations of the quantum accelerated motion.