Theoretical study of some bis-verdazyl diradicals: singlet–triplet energy gap

The bis-verdazyl diradical (BVD) system is closely examined by using the multiconfiguration wavefunctions as well as the density functional theory (DFT). The totally symmetric singlet ground state turns out to have strong multiconfiguration character at all levels of theory. The singlet ground state takes on the planar structure while the most stable triplet state corresponds to the twisted form. The MCSCF+MCQDPT2 calculations are shown to be sufficient to predict the singlet–triplet energy gap which is insensitive to the electronic characters of the ring substituents.     

Solvatochromic effects in the fluorescence and triplet—triplet absorption spectra of xanthone,thioxanthone and N-methylacridone

While the fluorescence of xanthone, thioxanthone and N-methylacridone shows the customary red shift with increasing solvent polarity, as measured by a polarization function, indicating an increase in dipole moment on excitation, the triplet-triplet (T₁T_n) absorption spectra are strongly blue shifted, indicating a decrease in dipole moment on excitation.     

The use of charge transfer complexing to elucidate some triplet—triplet spectra

From the excited state spectrum of chloranil complexes of some aromatic hydrocarbon charge transfer complexes it has been possible to obtain well-resolved spectra of T₁-T₂ transitions and to obtain a well-resolved T₁-T₂ spectrum of perylene.     

Triplet—triplet absorption and polarization spectra of phenazine

Employing laser photoselection spectroscopy, the triplet—triplet (T—T) polarization spectrum over the visible portion of the spectrum of phenazine was recorded. The strong T—T absorption band located in the violet portion of the spectrum is differently polarized from the flat band stretching from the blue to the red portion of the spectrum. This indicates the presence of two electronic transitions. The portion located in the violet spectral region is long-axis-polarized and presents the ³B⁻_3g ← ³B⁺_2u transition and the long-wavelength portion to the short-axis-polarized ³A⁻_1g ← ³B⁺_2u transition.     

Higher singlet and triplet n,π* states of glyoxal vapor

Several S_n(n,π^*) and T_n(n,π^*) states of glyoxal vapor with n ⩾ 2 were observed for the first time by two-color fluorescence dip and phosphorescence dip spectroscopies.     

Exploration of the π-electronic structure of singlet, triplet, and quintet states of fulvenes and fulvalenes using the electron localization function

The singlet ground states and lowest triplet states of penta- and heptafulvene, their benzannulated derivatives, as well as the lowest quintet states of pentaheptafulvalenes, either the parent compound or compounds in which the two rings are intercepted by either an alkynyl or a phenyl segment, were investigated at the (U)OLYP/6-311G(d,p) density functional theory level. The influence of (anti)aromaticity was analyzed by the structure-based aromaticity index HOMA, the harmonic oscillator model of aromaticity. The extent of (anti)aromatic character was also evaluated in terms of the π-electron (de)localization as measured by the π component of the electron localization function (ELF(π)). The natural atomic orbital (NAO) occupancies were calculated in order to evaluate the degree of π-electron shift caused by the opposing electron-counting rules for aromaticity in the electronic ground state (S(0); Hückel's rule) and the first ππ* excited triplet state (T(1); Baird's rule). Pentaheptafulvalene (5) shows a shift of 0.5 π electrons from the 5-ring to the 7-ring when going from the S(0) state to the lowest quintet state (Qu(1)). The pentaheptafulvalene 5 and [5.6.7]quinarene 7 were also investigated in their 90° twisted conformations. From our study it is apparent that excitation localization in fulvalenes, but not in fulvenes, to a substantial degree is determined by aromaticity localization to triplet biradical 4n π-electron cycles. Isolated benzene rings in these compounds tend to remain as closed-shell 6π-electron cycles.     

Bodipy–C60 triple hydrogen bonding assemblies as heavy atom-free triplet photosensitizers: preparation and study of the singlet/triplet energy transfer

Supramolecular triplet photosensitizers based on hydrogen bonding-mediated molecular assemblies were prepared. Three thymine-containing visible light-harvesting Bodipy derivatives (B-1, B-2 and B-3, which show absorption at 505 nm, 630 nm and 593 nm, respectively) were used as H-bonding modules, and 1,6-diaminopyridine-appended C₆₀ was used as the complementary hydrogen bonding module (C-1), in which the C₆₀ part acts as a spin converter for triplet formation. Visible light-harvesting antennae with methylated thymine were prepared as references (B-1-Me, B-2-Me and B-3-Me), which are unable to form strong H-bonds with C-1. Triple H-bonds are formed between each Bodipy antenna (B-1, B-2 and B-3) and the C₆₀ module (C-1). The photophysical properties of the H-bonding assemblies and the reference non-hydrogen bond-forming mixtures were studied using steady state UV/vis absorption spectroscopy, fluorescence emission spectroscopy, electrochemical characterization, and nanosecond transient absorption spectroscopy. Singlet energy transfer from the Bodipy antenna to the C₆₀ module was confirmed by fluorescence quenching studies. The intersystem crossing of the latter produced the triplet excited state. The nanosecond transient absorption spectroscopy showed that the triplet state is either localized on the C₆₀ module (for assembly B-1·C-1), or on the styryl-Bodipy antenna (for assemblies B-2·C-1 and B-3·C-1). Intra-assembly forward–backward (ping-pong) singlet/triplet energy transfer was proposed. In contrast to the H-bonding assemblies, slow triplet energy transfer was observed for the non-hydrogen bonding mixtures. As a proof of concept, these supramolecular assemblies were used as triplet photosensitizers for triplet–triplet annihilation upconversion.     

Mössbauer spectra of ferrous salts of transition metal cyano complexes. A survey

Ferrous salts of ten hexacyanometallates and three tetracyanometallates were obtained and their Mössbauer spectra interpreted according to recent structural models for these families of compounds. Ferrous ferrocyanide (Williamson White) and its ruthenium and osmium analogs prepared mechanochemically are stable for hours, allowing their study by Mössbauer spectroscopy and other related techniques. For ferrous salts of trivalent hexacyanometallate anions, the random distribution of anion vacancies is discarded and a model of two well defined relative positions of CN and H2O ligands around the Fe2+ is suggested. Iron was found octahedrally coordinated in tetracyanometallates.     

Theoretical study on the singlet and triplet potential energy surfaces of NH (X3Σ−) + HCNO reaction

Both the singlet and triplet potential energy surfaces (PESs) of the NH (X³Σ^?) + HCNO reaction have been investigated at the BMC-CCSD level based on the UB3LYP/6-311++G(d, p) structures. The results show that the title reaction is more favorable through the singlet potential energy surface than the triplet one. For the singlet potential energy surface of the NH (X³Σ^?) + HCNO reaction, the most feasible association of NH (X³Σ^?) with HCNO is found to be a non-barrier nitrogen-to-carbon attack forming the adduct a (trans-HNCHNO), which can isomerize to the adduct b (cis-HNCHNO). The most feasible channel is that the 1, 3-H shift with N2–H2 and C–N1 bonds cleavage associated with the N1–H2 bond formation of adduct a leads to the product P ₁ (HCN + HNO). Moreover, P ₂ (HNC + HNO) should be the competitive product. The other products, including P ₃ (NH₂ + NCO) and P ₄ (N₂H₂ + CO), are minor products. The product P ₁ can be obtained through two competitive channels Path 1: R → a → P ₁ and Path 3: R → b → d → P ₁ , whereas the product P ₂ can be formed through Path 2: R → b → d → P ₂ . At high temperatures, the nitrogen-to-nitrogen approach may become feasible. For the triplet potential energy surface of the NH (X³Σ^?) + HCNO reaction, the Path 10: R → ³ a → ³ a ₁ → P ₁ should be the most feasible pathway due to the less reaction steps and lower barriers. These conclusions will have impacts on further experimental investigations.     

Computational mechanistic investigation of the gas phase C2H4 + CO reaction on the singlet and triplet potential energy surfaces

Reaction pathways of ethylene and carbon monoxide on the singlet and triplet potential energy surfaces (PESs) have been calculated at B3LYP/6-311++G (3df, 3dp), G3B3 and CCSD(T)//B3LYP levels. Reaction mechanisms have been investigated by analysis of various structures. Suggested reaction mechanisms reveal that ³P3(CH₂CHCHO) and ³P4(CH₃CCHO) are thermodynamically stable adducts with the negative value in Gibbs free energies on the triplet PES. In addition, results show that one intersystem crossing exists between triplet and singlet PESs, which are obtained by scanning of the C–C bond length in ¹IN3 and ³IN7 species.     

Reproduction and interpretation of the UV–vis spectra of some flavonoids

The UV–vis spectra of 15 naturally occurring flavonoids, including flavones, flavonols, and isoflavones, were simulated and compared to literature experimental results. For this purpose, the TDDFT method in conjunction with the B3LYP-D3 and B3LYP functionals was applied. In spite of some discrepancy between the structural predictions, the differences between the TDDFT/B3LYP and TDDFT/B3LYP-D3 results are negligible. The performance of both functionals in reproducing the UV–vis spectra of the selected flavonoids is satisfactory. The NLMO clusters, i.e. molecular moieties characterised with distinguished electron density, were created. The combined results from the TDDFT and NLMO approaches were employed to perform deep analysis of the spectra. It was found that the transitions from the bonding NLMO clusters to the LUMO cluster are favoured at longer wavelengths, whereas the transitions from the HOMO and HOMO?1 clusters to the antibonding NLMO clusters are favoured at shorter wavelengths. All flavonoids show the HOMO → LUMO and HOMO?1 → LUMO transitions at long wavelengths, and majority of them show the HOMO → LUMO+1 transition at moderate wavelengths. This investigation confirms our earlier finding that the TDDFT and NBO approaches are complementary, implying that the results from the two theories can be combined to better understand the redistribution of electron density upon excitation.     

Analysis of optical absorption spectra of transition metal cluster ions by the spin-polarized DV-Xα method

Optical absorption spectra of cobalt cluster ions, Co _n ⁺ , and vanadium cluster ions, V _n ⁺ , were analyzed by a theoretical calculation based on the spin-polarized DV-Xα method, and their electronic and geometric structures were obtained. Relative absorption cross section associated with each electronic transition was calculated; the calculation enables a qualitative comparison of calculated spectrum with a measured one not only in its transition energy but also in its intensity profile. This analysis shows that Co ₄ ⁺ , Co ₃ ⁺ , and V ₄ ⁺ have, respectively, a tetrahedral structure with a bond distance of 2.00Å, an equilateral triangle with a bond distance of 2.30Å, and a distorted tetrahedral structure with five bonds having a distance of 2.34 Å and one of 2.89Å. The differences in the population between majority and minority spins (spin-difference) evaluated from the electronic structure thus obtained were 2.0, 1.7, and zero per atom in Co ₃ ⁺ , Co ₄ ⁺ , and V ₄ ⁺ , respectively. These spin differences indicate a ferromagnetic and an antiferromagnetic spin-coupling in the cobalt and vanadium cluster ions, respectively.     

On the extraction of spectra of components from spectra of mixtures. A development in factor theory—II

The theory of factor analysis developed in Part I [A. Muller and D. Steele, Spectrochim. Acta 46A, 817 (1990) [1] is extended to cases where m > 3, m being the number of factors. The effect of increasing the number of independent parameters by m(m-1) for T′ and the subsequent changes produced in the transformed eigenspectra, are investigated. Applications to actual spectra of mixtures of: (A) butan-2-one, ethyl ethanoate, cyclohexane and oct-1-ene (B) butan-2-one, ethyl ethanoate, cyclohexane and 2-methylpentane and (C) oct-1-ene, butan-2-one, ethyl ethanoate, cyclohexane and 2-methyl-pentane are presented. Using standard target techniques, an alternative approach is developed for the m> 3 case. This is based on transformation of the leading three eigenspectra, followed by identification and elimination of a component in a repetitive manner, until completion. The problems associated with the implementation of the Beer-Lambert Law are explored the need for accurate determination of a suitable wavenumber block to ensure the removal of the correct amount of each component, is examined. The ability to recognize at least one of the m component spectra per programme cycle is demonstrated.     

On the extraction of spectra of components from spectra of mixtures. A development in factor theory—I

The theory of factor analysis is extended to permit the computer based extraction of the spectra of pure components from spectra of mixtures. A simultaneous linear, non-orthogonal transformation of the eigenspectra and eigenvectors is used to generate all positive absorbances and concentrations within noise level. Applications to actual spectra of mixtures of: (A) ethyl ethanoate, butan-2-one and oct-1-ene; (B) ethyl ethanoate, butan-2-one and cyclohexane; and (C) butan-2-one, cyclohexane and 2-methylpentane are presented. The effects of changes in signs of the constrained diagonal elements of the transformation matrix is investigated. To explore the ability of the software to cope with component spectra in which there are no wavenumbers at which one component dominates an artificial set of mixtures is examined. Recognizable spectra are extracted. It appears that, even when there are no wavenumbers at which one component dominates, the condition of finding “the sum of squares of negative absorbances/concentrations” near zero is adequate to yield useful spectra for library searches.     

Structure of the lowest triplet states of poly-α-methylstyryl sodium.Ab initio calculations

Ab initio optimization of a poly-α-methylstyryl sodium (PMSNa) fragment consisting of two eis units yields a triplet state energy which is close to the ground state energy. A new mechanism is proposed for depolymerization of “living” polymers, which implies that an elementary step involves excitation to the low-lying triplet state with a charge transfer and with further bond cleavage. In the reaction structure, electronic excitation occurs with a minor (≈0.5 Å) displacement of the Na⁺ cation between the last and the last but one monomer units. The reversible polymerization/depolymerization reaction of PMSNa in THF was studied experimentally. The experimental (5.6 kcal/mole) and calculated (7.3 kcal/mole) polymerization enthalpies are in reasonable agreement.     

Influence of the anisometry of magnetic particles on the isotropic–nematic phase transition

The influence of the shape anisotropy of magnetic particles on the isotropic–nematic phase transition was studied in ferronematics based on the nematic liquid crystal (LC) 4-(trans-4-n-hexylcyclohexyl)-isothiocyanato-benzene (6CHBT). The LC was doped with spherical or rod-like magnetic particles of different size and volume concentrations. The phase transition from isotropic to nematic phase was observed by polarising microscope as well as by capacitance measurements. The influence of the concentration and the shape anisotropy of the magnetic particles on the isotropic–nematic phase transition in LC are demonstrated here. The results are in a good agreement with recent theoretical predictions.     

Synthesis,structure and chiroptical spectra of the bicyclic α-diketones,imides and dithioimides related to santenone

Isomeric α-diketones, imides and dithioimides related to santenone were prepared in a multistep synthesis from (+)-camphor and their CD spectra compared with those of analogous chromophoric systems related to camphor. In the case of conformationally rigid α-diketones the methyl substituents at C-7, lying on the symmetry plane of the chromophore, exert only a weak contribution to the n–π* Cotton effects. In contrast, the Cotton effect magnitudes of the anhydrides, imides and dithioimides are significantly affected by the substituents at C-8. The steric interaction of these chromophores with the syn-methyl group at C-8, leading to the chromophore distortion, was confirmed by X-ray crystallographic studies.     

Optical spectroscopy methods for the characterization of sol–gel materials

Journal of Sol-Gel Science and Technology - In this paper, structural, optical, and electrical features of undoped and copper-incorporated nickel oxide (Cu/NiO) films with different mole ratios...