Theoretical calculations on radiative and nonradiative processes of quartet states of HeH

MRD CI calculations have been carried out on the lowest four ⁴Σ⁺ and the lowest two ⁴Π states of HeH. Potential energy curves, rates of radiative transitions and also rates of predissociation by radial coupling have been obtained, in order to make predictions on the possibility of observing quartet spectra in HeH.     

A method for the calculation of transition moments between electronic states of molecules using a different one-electron basis set for each state

A state-specific approach to the calculation of transition moments between molecular electronic states requires that the wavefunction for each state is expanded in its optimum one-electron basis and that nonorthonormal basis techniques are used for the calculation of the transition moment integrals. A method has been developed for carrying out such nonorthonormal basis calculations, based on the corresponding orbitals transformation and appropriately defined density matrices, which may be used with configuration interaction (CI ) wavefunctions. Further improvements of the method have resulted in a decrease in the time required for the calculations and thus allow its application with moderately large CI expansions for each state. Nonorthonormal basis calculations on transition moments in H₂O have been carried out using the above method. The results are in agreement with those of large MRD -CI calculations.     

Theoretical and experimental ionization potentials of (CH3)2S and (CH3)2SO. The effect of substituents R on the sulphur ESCA shifts in the series R2S, R2SO, R2SO2

Theoretical and experimental inner shell ionization potentials (IP) have been determined for (CH₃)₂S and (CH₃) ₂SO. This information is combined with other data to draw conclusions on the effect of methyl and phenyl substituents in the series R₂S, R₂SO and R₂SO₂, on the chemical shifts of the sulphur ²P IP. It was found that while methyl substitution has no significant effect on the chemical shifts of the sulphur ²P IP, phenyl substition modifies them significantly implying a donation of electron density from the phenyl groups to sulphur.     

Bending potentials for H2O in the ground and the first six singlet excited states

MRD CI calculations are presented for the bending potentials of H₂O in the ground and first six singlet excited states. The results are discussed with reference to the H(²S) + OH(A ²Σ⁺) dissociation path of H₂O.     

Investigation of Inhomogeneites in Epitaxial AlxGa1−xN Layers Grown on Sapphire

 Procedures for the preparation of bevels and the determination of their geometrical parameters have been developed. Using these procedures study of compositional and optical spatially resolved inhomogeneities of Al_xGa_1−xN layers grown on (0001) sapphire have been studied by EPMA and cathodolu-minescence. It has been found that the nonuniform distribution in depth of Al in epitaxial layers grown under constant conditions is connected with presence of stresses in the layer.     

An ab initio potential energy surface and spectroscopic constants for the XΣg state of NO2

A three-dimensional potential energy function has been calculated for the X¹Σ⁺_g state of NO⁺₂ from ab initio MRD-CI data. With this PE function, converged vibrational calculations have also been performed for ten vibrational states, with the aid of a computer program developed in the present work for this purpose. The calculated harmonic frequencies, vibrational term values and rotational constants are in good agreement with experimental data.     

The solvent effect on a styryl-bodipy derivative functioning as an AND molecular logic gate

We study via DFT and TDDFT calculations the photophysical processes of a styryl-bodipy derivative, ( 1 ), of its monometallic complexes 1-M ²⁺ (M = Ca, Zn, and Hg), and its trimetallic complex ( 2 ) unprotonated, protonated and complexed with water molecules in water solvent and in acidic conditions. The main targets of this study are to gain information regarding published reports on fluorophore species mentioning that fluorescent switching results from trace water, to study how 1 behaves in water solvent which is a common used solvent for molecular logic gates (MLG), and how it behaves in acidic conditions. We conclude that in water solvent, as in acetonitrile solvent (which was found before both theoretically and experimentally) there will be a quenching of emission spectra in 1 and 1-M ²⁺ and a retaining of emission in 2 . However, contrary to acetonitrile solvent, in water, a weak peak will be observed for 1 and 1-M ²⁺ , due to a small ratio of reversible protonation, showing that in acetonitrile 1 acts as a better MLG candidate than in water solvent. On the other hand, in acidic conditions all five species will emit and as a result, 1 will not be an AND MLG, showing that the selection of the solvent conditions is crucial for a species to act as an MLG candidate. Finally, we conclude that the retaining of emission is accomplished by the simultaneous tetrahedral geometry of all three aniline N atoms.     

Computational insight into the electronic structure and absorption spectra of lithium complexes of N-confused tetraphenylporphyrin

The present work is a theoretical investigation on lithium complexes of N-confused tetraphenylporphyrins (aka inverted) employing density functional theory (DFT) and time-dependent DFT, using the B3LYP, CAM-B3LYP, and M06-2X functionals in conjunction with the 6-31G(d,p) basis set. The purpose of the present study is to calculate the electronic structure and the bonding of the complexes to explain the unusual coordination environment in which Li is found experimentally and how the Li binding affects the Q and the Soret bands. The calculations show that, unlike a typical tetrahedral Li(+) cation, this Li forms a typical bond with one N and interacts with the remaining two N atoms, and it is located in the right place to form an agostic-like interaction with the internal C atom. The reaction energy, the enthalpy for the formation of the lithium complexes of N-confused porphyrins, and the effect of solvation are also calculated. The insertion of Li into N-confused porphyrin, in the presence of tetrahydrofuran, is exothermic with a reaction energy calculated to be as high as -72.4 kcal/mol using the lithium bis(trimethylsilyl)amide reagent. Finally, there is agreement in the general shape among the vis-UV spectra determined with different functionals and the experimentally available ones. The calculated geometries are in agreement with crystallographic data, where available.     

Electronic structure and absorption spectra of supramolecular complexes of a fullerene crown ether with a π-extended TTF derivative

The present work is a theoretical investigation on supramolecular complexes of a fullerene crown ether (A and B isomers) with a derivative of π-extended tetrathiafulvalene (T). The geometry and the electronic structure of seven different conformers of the complex of dibenzo-18-crown-6 ether of fullero-N-methylpyrrolidine with a N-benzyl-N-(4-{[9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracen-2-yl]ethynyl}benzyl)ammonium cation were determined. We calculated the complexation energies and the absorption spectra, i.e., the lowest 50 excited electronic states of the complexes have been determined at the ground state optimum geometry. All calculations were carried out employing the density functional theory (DFT) and the time-dependent DFT, using the B3LYP, CAM-B3LYP, ωB97X-D, and M06-2X functionals in conjunction with the 6-31G(d,p) basis set. Various types of van der Waals interactions are observed in the complexes. Conformer complexation energies (CE) range from 2.54 to 2.14 eV in the gas phase and from 1.75 to 1.34 eV in CHCl(3) solvent at the ωB97X-D/6-31G(d,p)//M06-2X/6-31G(d,p) level of theory. There are three major features at about 390, 330, and 290 nm in the calculated absorption spectra of all the conformers. The major peaks correspond to T→T, T→T/F (electron density in both T and the fullerene F of B) and to T→F transitions, depending on the particular conformer. Other charge transfer T→F transitions are observed close to the T→T transition, indicating the possibility of photoinduced electron transfer in all these complexes.     

s-Representations for involutions¶on affine Kac–Moody algebras are polar

Let denote the eigenspace decomposition of a twisted affine Kac–Moody algebra with respect to an involution , where is a twisted loop algebra, is the center and d is the scaling element of . We endow with the standard bilinear symmetrical form.Then with and carries a Lorentzian signature. Let denote the group that corresponds to , then the adjoint representation of on can be restricted to and this submanifold is isometrical to the Hilbert space E _ε, where is the decomposition of the twisted loop algebra with respect to the induced involutionρ₀.We thus obtain an affine representation on E _ε and we show that this representation is polar, i. e., there exists a submanifold that intersects all orbits, and intersects them orthogonally. Received: 16 February 2000 RID=" ID="Supported by a DFG grant.