Molecular applications of the intermediate Hamiltonian Fock-space coupled-cluster method for calculation of excitation energies

The intermediate Hamiltonian Fock-space coupled-cluster (FS-CC) method with singles and doubles is applied to calculate vertical excitation energies (EEs) for some molecular systems. The calculations are performed for several small molecules, such as H2O, N2, and CO, and for larger systems, such as C2H4, C4H6, and C6H6. Due to the intermediate Hamiltonian formulation, which provides a robust computational scheme for solving the FS-CC equations, and the efficient factorization strategy, relatively large basis sets and model spaces are employed permitting a comparison of the calculated vertical EEs with the experimental data.     

meso-tetrakis[2.2]paracyclophanylporphyrin: Electronic structure and electrochemical behavior

Replacement of all phenyl groups in meso-tetraphenylporphyrin, TPP, by [2.2]paracyclophane, PCP, enhances the increase of energy of the HOMO and HOMO-1 of porphine, P, already noticed for the mono-[2.2]paracyclophanyl-substituted TPP, and fills the energy gap by the occupied MOs of the PCP units. The first oxidation half-wave potential is respectively decreased to 0.52 V. The CNDO/S-CIS calculations agree with the experimental bathochromic shifts of all bands in the electronic spectra of the considered atropoisomers of the title compound, TPCPP, as compared to TPP. In the excited B states the interactions between the PCP and porphine units are represented mainly by the charge transfer of 0.44 e from PCP to P, according to transition density matrix calculations. While electroreduction of the title compound results in a successive formation of the anion radical and dianion, oxidation represents a four-step process involving one electron transfer per step, and resulting in the oxidation of two PCP units. Formation of the conductive polymeric film on the electrode seems to be connected with the transient formation of a quinoid system of bonds.     

Synthesis of porphyrinyl-nucleosides

Several porphyrinyl-nucleosides were prepared in the reaction of the OH group of one, two or four meso-p-hydroxyphenyl substituents of porphyrin with 5′-O-tosylates of 2′,3′-O-isopropylidene-adenosine or -uridine, or 5′-O-tosylthymidine; the remaining porphyrin meso-substituents were p-tolyl, p-hydroxyphenyl or 4-pyridyl. The following porphyrinyl-nucleosides were obtained with 8–17% yield: meso-di(p-tolyl)di(p-phenylene-5′-O-2′,3′-O-isopropylidene-adenosine) (or -uridine)porphyrins 1,2 , the respective meso-tetranucleosideporphyrins 3,4 -meso-mono(p-phenylene-5′-O-thymidine)porphyrins 5–7 , meso-di(p-tolyl)di(p-phenylene-5′-O-thymidine)porphyrins 8,9 and the meso-di(p-hydroxyphenyl)di(p-phenylene-5′-O-thymidine)porphyrins 10. Other compounds prepared belonged to the series: meso(4-pyridyl)_4?n(p-phenylene-5′-O-2′,3′-O-isopropylideneuridine)_nporphyrin, n = 1, 2 or 4, 11–13. N-Methylation gave the water soluble iodide salts: (N-methyl-4-pyridinium)4_4?n(p-phenylene-5′-O-2′,3′-isopropylideneuridine)_nporphyrins, n = 1, 2 or 4, 14–16. The ms fab showed in most cases stepwise detachment of the CH₂(5′)-nucleoside fragments. The porphyrins meso disubstituted by thymidine represent a convenient substrate for the build-up of both nucleoside units into the oligo/polynucleotide chains.     

The Triebel - Lizorkin Scale of Function Spaces for the Fourier - Helgason Transform

We define and investigate the Triebel - Lizorkin scale of function spaces F, with 1< p < ∞, 1< q ≤ ∞ for the Fourier-Helgason transform on symmetric Riemannian manifolds of the noncompact type.     

Vector-valued Fourier multipliers on symmetric spaces of the noncompact type

LetX be a Riemannian symmetric space of the noncompact type. We prove the multiplier theorem for the Helgason-Fourier transform and the vector valued function spacesL _p (X, l _q ). As a consequence we get the inequalities of the Littlewood-Paley type forL _p (X) spaces.Research supported by K.B.N. Grant 210519101 (Poland).     

Long-wavelength behavior of the optimal HNC/0 solution for the ground state

The set of Euler-Lagrange equations for the ground state of a symmetric film of liquid⁴He atT=0 K is solved. The optimal two-body correlation factor is determined by applying a recently proposed finite-difference relaxation method to equations formulated within the framework of the paired-phonon analysis. A relationship between the two-body correlation factor at the center of the film and that corresponding to bulk liquid is suggested. Numerical results for a rather thick film supported by an external potential are reported. A good overall agreement between results for non-uniform and uniform systems is found at the middle of the film. In particular, the long-wavelength behavior (i.e., for small momentumq parallel to the symmetry plane) of the optimal two-body correlation factor is in accord with an expression proportional toK ₀ (aq) derived from the asymptotic bulk Jastrow function. This analytic form in terms ofK ₀ leads to the correct behavior of the liquid structure functionS(q) at smallq in the limiting case of a film of infinite width.     

X-ray structure of isomeric 3-chloro-4-(methylthio)- and 4-chloro-3-(methylthio)quinolines

The crystal and molecular structures of two isomeric 3,4- and 4,3-chloro-(methylthio)quinolines have been determined. For 3-chloro-4-(methylthio)-quinoline (3-Cl–4-MeS–Q); triclinic, space group ,a=7.199(3),b=7.919(3),c=8.921(3) Å, =89.74(3), =74.29(3), =78.55(3)°. For 4-chloro-3-(methylthio)quinoline (4-Cl–3-MeS–Q): monoclinic, space group P2₁/n,a=12.860(4),b=5.424(2),c=13.434(4) Å, =90.84(3)°. The values of the Cl...S distance as well as those for the Cl–C–C(S) and (Cl)C–C–S angles indicate the attractive interaction between ortho-situated heteroatoms in isomer 4-Cl–3-MeS–Q contrary to the effects observed in the case of 3-Cl–4-MeS–Q. The conclusions were confirmed by calculations of atomic charges withab initio method 4-31G basis set, which show positively charged sulfur atom in 4-Cl–3-MeS–Q and negatively charged sulfur in 3-Cl–4-MeS–Q.Part XXX in the series of Azinyl Sulfides.     

Progress in MOCVD growth of HgCdTe heterostructures for uncooled infrared photodetectors

This paper describes the significant progress in the development of metalorganic chemical vapour deposition of Hg_1−xCd_xTe (HgCdTe) multilayer heterostructures on GaAs/CdTe substrates for uncooled infrared photodetectors. The paper focuses on the interdiffused multilayer process (IMP). The optimum conditions for the growth of single layers and complex multilayer heterostructures have been established.

One of the crucial stages of HgCdTe epitaxy is CdTe nucleation on GaAs substrate. Successful composite substrates have been obtained with suitable substrate preparation, liner and susceptor treatment, proper control of background fluxes and appropriate nucleation conditions. Epiready (1 0 0) GaAs wafers with 2–4° disorientation towards 1 0 0 and 1 1 0 have been used. Due to the large mismatch between GaAs and CdTe, both (1 0 0) and (1 1 1) growth may occur. Generally, layers with orientation (1 0 0) show superior morphology compared to (1 1 1), but they are also characterized by hillocks.

The benefits of the precursors, ethyl iodine (EI) and arsine (AsH₃), for controlled iodine donor doping and arsenic acceptor doping at dopant concentrations relevant for HgCdTe junction devices are summarized. In situ anneal seems to be sufficient for iodine doping at any required level. In contrast, efficient As doping with near 100% activation requires ex situ anneal at near saturated mercury vapours.

Finally, the multilayer fully doped heterostructures for photovoltaic devices operated at room temperature have been fabricated. The special attention is focused on the improvement in multijunction LWIR photovoltaic detectors. The performance of photodiodes is also presented.     

Numerical Analysis of Strains and Stresses in Stretched Specimens at Microstructure Level

In the paper an incremental methodology was proposed for the determination of the states of stresses and strains in specimens while taking into account the strain history and the strain rate history during a tension stress, and a new methodology to determine mechanical characteristics of metal materials. An equation of motion and deformation of the specimen was introduced while using a variational formulation and the finite element method. The results of numerical simulations which illustrate the methods proposed, were presented. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)