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1990 (227)
21Author    S. A. Kirillov, D. TunegaRequires cookie*
 Title    Peculiarities of the Ionic Dynamics of Molten Nitrites  
 Abstract    Polarization measurements in the Raman spectra of molten sodium nitrite have shown that the reorientational line widths of the v t and v 2 bands (both of the A 1 symmetry type) of N0 2 are different. Possible reasons are discussed. Also, the line widths of N0 2 for various molten nitrites are found to depend on R " 4 , the cloasest approach distance in the melt, and on Z, the cation charge number. This dependence agrees with theoretical predictions for the coupling of vibrational and reorientational dephasing caused by ion-dipole interactions. 
  Reference    Z. Naturforsch. 45a, 145—147 (1990); received September 27 1989 
  Published    1990 
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 Identifier    ZNA-1990-45a-0145 
 Volume    45 
22Author    Wolfhard KochRequires cookie*
 Title    Extended-Hückel Energy Band Structures of Organometallic Compounds with One-Dimensional Crystal Geometries Computational Results for Bis(2,5-dimethyl-N,N'-dicyanoquinonediimine) copper, -silver, and -lithium  
 Abstract    In order to rationalize the high electrical conductivity of 2,5-dimethyl-N,N'-dicyanoquinone-diimine radical anion salts (2,5-DM-DCNQI) of copper, silver, and lithium, we performed one-dimensional energy band structure calculations of extended-Hückel type (namely Self-Consistence of Charge, SCC) for one-dimensional models of these "organic conductors". In each case, SCC yields two overlapping incompletely occupied valence bands, which give rise to some evidence for the observed high electrical conductivity, in spite of the one-electron nature of the method. Furthermore, these two frontier energy bands do not contain any metallic orbital contribution, which suggests that the electron transport takes place in the organic stack of the 2,5-DM-DCNQI ligands only. 
  Reference    Z. Naturforsch. 45a, 148—156 (1990); received November 2 1989 
  Published    1990 
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 Identifier    ZNA-1990-45a-0148 
 Volume    45 
23Author    Nikola Getoff, MatthiasW. Haenel, Knut Hildenbrand, Udo-Burckhard Richter, Sonja Solar, D. RuhrRequires cookie*
 Title    Stabile Radikalanionen von Aromaten: Strahlenchemische Erzeugung in Gegenwart von Natrium-dihydrido- bis(2-methoxyethoxy) aluminat  
  Reference    Z. Naturforsch. 45a, 157—160 (1990); received November 14 1989 
  Published    1990 
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 Identifier    ZNA-1990-45a-0157 
 Volume    45 
24Author    Thomas Schönherr, Joachim DegenRequires cookie*
 Title    Electronic Spectra and an Angular-Overlap-Model Analysis of fra/!s-[Cr(ox) 2 (py) 2 ]~  
 Abstract    The quartet and doublet transition in frans-[Cr(ox) 2 (py) 2 ]~ show considerable band splittings due to the low-symmetry of the ligand field. The components of 2 E g (O h) and 2 T lg (O h) have been assigned by analysis of vibrational sideband structures in the low-temperature absorption and emission spectra. The energy level scheme has been rationalized in terms of the angular-overlap model. The different contributions of n bonding from the oxalate (n donor) and pyridine (n acceptor) ligands give an explanation of the uncommon quartet band splittings. The doublet energies depend strongly on the molecular geometry. In particular, a reduction of the oxalate bite angle to about 84° has been derived from the spectral band fit. 
  Reference    Z. Naturforsch. 45a, 161—168 (1990); received October 10 1989 
  Published    1990 
  Keywords    Angular-overlap model, Chromium (III) complexes, Vibronic spectra, Spectrum-struc-ture correlations 
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 TEI-XML for    default:Reihe_A/45/ZNA-1990-45a-0161.pdf 
 Identifier    ZNA-1990-45a-0161 
 Volume    45 
25Author    S. Sengteller, H. L. Selzle, E. W. SchlagRequires cookie*
 Title    Study of the Metastable Decay of Single Size Benzene Clusters by an Ion Stopping Technique  
 Abstract    A method has been developed which allows to stop single sized cluster ions in a superionic jet. This cluster will stay isolated in space for a long time and photochemical processes can be studied without perturbation from the other clusters in the jet. This allows to uniquely identify the parent complex, and the metastable decay of this complex can be analyzed. 
  Reference    Z. Naturforsch. 45a, 169—172 (1990); received January 9 1990 
  Published    1990 
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 Identifier    ZNA-1990-45a-0169 
 Volume    45 
26Author    Jorma HölsäRequires cookie*
 Title    Parametrization of Crystal Field Splittings of the 7 F 7 Levels in Eu 3+ Doped Tetragonal Rare Earth Oxyhydroxides, REOOH:EU 3+ (RE = Y and Lu)  
 Abstract    The luminescence spectra of europium (3 +) doped rare earth oxyhydroxides, REOOH :Eu 3 + (RE = Y and Lu), were studied and analyzed at 77 and 300 K under UV and dye laser excitation. The observed 7 F 0 _ 4 level schemes were simulated with the aid of the phenomenological crystal field theory. The descending symmetry method from C 2v to C s symmetry was used in the simulation. Good results were obtained with C s symmetry simulation which yielded r.m.s. deviations of 6 and 7 cm -1 between the calculated and experimental 7 F 0 _ 4 level schemes for YOOH:Eu 3+ and LUOOH:EU 3+ , respectively. The C 2v simulation was found inadequate to describe the experimental energy level schemes. The even rank crystal field parameters vary only slightly as a function of the host. Comparison with the corresponding values obtained for the monoclinic form of the Eu 3 + doped RE oxyhydroxides reveals significant differences. 
  Reference    Z. Naturforsch. 45a, 173—178 (1990); received October 23 1989 
  Published    1990 
  Keywords    Crystal field, Europium, Rare earth oxyhydroxides 
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 Identifier    ZNA-1990-45a-0173 
 Volume    45 
27Author    B. Marciniak, H. Kozubek, J. Koput, S. PaszycRequires cookie*
 Title    Spectroscopic and Photochemical Studies of Gossypol in Solution  
 Abstract    Spectroscopic properties of gossypol and its stability in different solvents and pH are studied by means of UV-visible absorption and emission spectroscopy. The results are correlated and discussed on the basis of semiempirical INDO/S CI calculations. The influence of oxygen and excitation wavelength on the photodecomposition of gossypol in solution is also investigated. 
  Reference    Z. Naturforsch. 45a, 179—183 (1990); received October 10 1989 
  Published    1990 
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 Identifier    ZNA-1990-45a-0179 
 Volume    45 
28Author    Saiful Islam, E.H S Anwander, M. M. Probst, B. M. RodeRequires cookie*
 Title    Intermolecular Potential Function for Copper (II)-Water Based on ab initio Calculations  
 Abstract    An analytical pair potential function for the system Cu(II)-water has been derived by means of ab initio calculation of the corresponding energy surface, using double zeta + polarization basis sets and effective core potentials. Tests on the function show that it should be reliable for use in Monte Carlo or molecular dynamics simulations. 
  Reference    Z. Naturforsch. 45a, 184—188 (1990); received November 6 1989 
  Published    1990 
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 Identifier    ZNA-1990-45a-0184 
 Volume    45 
29Author    J. Waite, M. G. PapadopoulosRequires cookie*
 Title    The Effect of the H-Bond Interactions on the First Hyperpolarisability of (HF)". A Comparative Study  
 Abstract    The effect of H-bond interactions on the first hyperpolaris-ability (ß) of (HF)" is discussed. The reported results confirm, computationally, the remarkable sensitivity of this property to intermolecular interactions, which has been found experi-mentally. Results for the second hyperpolarisability (y) and the total energy (£) are also presented for comparative pur-poses. The analysis is based on data calculated by the CHF-PT-EB-CNDO method. 
  Reference    Z. Naturforsch. 45a, 189—190 (1990); received November 13 1989 
  Published    1990 
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 Identifier    ZNA-1990-45a-0189_n 
 Volume    45 
30Author    R.M S Radius, C. G. KoutroulosRequires cookie*
 Title    An Estimate of the of the ls-State Orbital of the A-Particle in Hypernuclei  
  Reference    Z. Naturforsch. 45a, 191—192 (1990); received November 9 1989 
  Published    1990 
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 Identifier    ZNA-1990-45a-0191_n 
 Volume    45 
31Author    Alarich Weiss, Silvia WigandRequires cookie*
 Title    Correlation of NQR and Chemical Bond Parameters  
 Abstract    Nuclear quadrupole resonance is an effective spectroscopic method to investigate the charge density distribution in solids. The range of compounds which may be investigated is wide, reaching from a crystal lattice built up by an ordered arrangement of neutral molecules in the crystalline material to ionic crystals and to metallic solids. First the correlations between NQR quantities and bond parameters which become apparent from the molecular orbital picture will be discussed, e.g. Hammett a, x-parameter, ionic character i, s-character, ionicity, electronegativity in their connection to NQR. Then, the correlations of NQR frequencies, respectively nuclear quadrupole coupling constants, with bond lengths and bond angles are considered. Cross correlations, e.g. of NQR frequencies with bond distances, bond distances with vibrational frequencies, and vibrational frequencies with NQR frequencies are discussed as are pK A dependen-cies of NQR parameters. The connection of e<P z ,Qh~ 1 (14 N) in pharmaceuticals with their biolog-ical activity is pointed out. 
  Reference    Z. Naturforsch. 45a, 195—212 (1990); received August 9 1989 
  Published    1990 
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 Identifier    ZNA-1990-45a-0195 
 Volume    45 
32Author    ValentinP. Feshin, MikhailG. VoronkovRequires cookie*
 Title    The EFG Asymmetry Parameters at 3 5 CI Nuclei and the Electronic Effects in Chlorine-Containing Organic and Complex Compounds of Group IVA and VA Elements  
 Abstract    The 35 C1 NQR method and, in particular, the EFG asymmetry parameters at 35 C1 nuclei were used for the solution of a number of principal problems of theoretical organic and organometallic chemistry, such as the mechanism of non-induction influence of the heteroatom M on the atom Y in the non-linear Y-Z-M or Y-Z = M group, M-Cl bond multiplicity in planar molecular frag-ments and the asymmetry of halogen atom electron distribution in organic and organometallic molecules. In tetrahedral molecules this distribution is nearly axially symmetric for different M. This symmetry is also characteristic for axial chlorine atoms in trigonal-bipyramidal and octahedral molecules, independently of M. The deviation of the electron distribution of equatorial chlorine atoms from axial symmetry in the two latter cases depends essentially upon M and does not depend much on the peculiarity of the formation of these polyhedra and the character and number of substituents. 
  Reference    Z. Naturforsch. 45a, 213—218 (1990); received August 23 1989 
  Published    1990 
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 Identifier    ZNA-1990-45a-0213 
 Volume    45 
33Author    ValentinP. Feshin, GennadiiV. Dolgushin, IgorM. Lazarev, Mikhail, G. VoronkovRequires cookie*
 Title    The Structure of Tetrachlorostannate Complexes with Ketones from 35 C1 NQR Data  
 Abstract    35 C1 NQR spectra (77 K) of 1:1 and 2:1 RR'CO-SnCl 4 are recorded and discussed. These spectra change in the course of time. At low temperatures either octahedral or trigonal-bipyramidal com-plexes (depending on the ratio of components and the nature of ligands) are formed. Frequently these systems contain a mixture of steric isomers or a mixture of complexes having different coordination numbers of the tin atom. In the solid state some complexes show a transition from one to another configuration. 
  Reference    Z. Naturforsch. 45a, 219—223 (1990); received August 23 1989 in revised form December 29 1989 
  Published    1990 
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 Identifier    ZNA-1990-45a-0219 
 Volume    45 
34Author    Augustin Habiyakare, EdwinA C LückenRequires cookie*
 Title      
 Abstract    The NQR frequencies of the 63 65 Cu nuclei in di-coordinated complex cations of Cu 1 , having the general formula CuL 2 X, where L is a substituted pyridine and X is a hard anion such as C10 4 , are reported and discussed in the light of the known crystal structures. A departure from a strictly linear geometry of the L 2 Cu cation has but little effect on the resonance frequency, but the donor-acceptor bond between the nitrate anion and the copper atom in bis(2,6-lutidine)cuprous nitrate, which was postulated on crystallographic grounds, is confirmed by the NQR results, which also indicate a similar interaction in bis(2,6-lutidine)cuprous trifluoroacetate. A number of the complexes discussed here have not been reported previously. 
  Reference    Z. Naturforsch. 45a, 224—228 (1990); received October 23 1989 
  Published    1990 
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 Identifier    ZNA-1990-45a-0224 
 Volume    45 
35Author    Peter Storck, Norbert Weiden, Alarich WeissRequires cookie*
 Title    The Bond Sn-Cl in Sn IV Complex Salts A 2 [(C 2 H 5 )SnCl 5 l. A Single Crystal 3 5 CI NQR Study of Bis(methylammonium)- pentachloroethylstannate, (CH 3 NH 3 ) 2 |(C 2 H 5 )SnCl 5 ]  
 Abstract    Zeeman 35 C1 NQR spectroscopy has been applied to determine the magnitude and orientation of the EFG tensors at the chlorine sites in a single crystal of(CH 3 NH 3) 2 [(C 2 H 5)SnCl 5 ] at 293 K. The assignment of the NQR frequencies v ; (35 Cl), the corresponding quadrupole coupling constants eQfP^h^ 1 , and the asymmetry parameters f/,(35 C 1) to certain Cl (k ' atoms is discussed. The most probable assignment is (no. i of v,(35 Cl), v,(35 Cl)/MHz, eQ$ { ? z r'/MHz, f7, (35 Cl), no. k of assigned Cl w , d(Sn-Cl" I))/pm, * (<P% d(Sn-Cl w)): »' = 1,17.032, 34.046,0.056, k= 1, 242.6, 3.1°; i = 2, 12.072, 24.089, 0.117, k = 3, 250.7, 1.9°; i = 3, 11.537, 22.992, 0.146, k = 2, 253.1, 2.8°; i = 4, 10.770, 21.455, 0.154, k = 4, 249.7, 2.9 °; i = 5,9.969,19.842,0.171, k = 5,254.9,1.7The orientation of the tensor axes <P { jj,j = x, y, z, i= 1 -5, in space is mainly determined by the geometry of the [(C 2 H 5)SnCl 5 ] 2e anion. The <t>f z are nearly parallel to the assigned bond directions Sn-Cl (,I) . >y(35 CI) is low, increasing with decreasing v(35 Cl). The reason for the asymmetry seems not to be a rc-character in the Sn-Cl bond, but the charge distribution within the anion. The rule that a longer bond corresponds to a lower NQR frequency is valid as a general tendency, but not strict. 
  Reference    Z. Naturforsch. 45a, 229—236 (1990); received August 21 1989 in revised form November 15 1989 
  Published    1990 
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 Identifier    ZNA-1990-45a-0229 
 Volume    45 
36Author    Hideta Ishihara, Shouko Nakashima, Koji Yamada, Tsutomu Okuda, Alarich WeissRequires cookie*
 Title    NQR Study of AlBr 3 Complexes with Donor-Acceptor O-Al Bond  
 Abstract    81 Br and 27 A1 NQR were observed in AlBr 3 complexes with 4-XC 6 H 4 NO,(X = H, CI, Br, I, CH 3 , and C 2 H 5), C 6 H ? COBr, (C 6 H 5) 2 CO, and (C 2 H 5) 2 0. In the 4-XC 6 H 4 NÖ 2 complexes, the 27 A1 quadrupole coupling constants (QCC's) were well correlated with the Hammett er p 's of the para-sub-stituents, i.e., electron-withdrawing groups caused reduction of the charge density of O-Al bonds which resulted in large 2 Al QCC's and vice versa. The temperature dependences of the 8 'Br NQR frequencies and quadrupolar spin-lattice relaxation times showed that the 4-C 2 H 5 C 6 H 4 N0 2 and C 6 H 5 COBr complexes undergo phase transitions at 154 K and around 200 K, respectively, and show hindered rotation of the AlBr 3 groups at higher temperatures, and that the (C 2 H 5) 2 0 complex reorients above ca. 120 K. 
  Reference    Z. Naturforsch. 45a, 237—242 (1990); received August 22 1989 in revised form November 15 1989 
  Published    1990 
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 Identifier    ZNA-1990-45a-0237 
 Volume    45 
37Author    Gary Wulfsberg, Norbert Weiden, Alarich WeissRequires cookie*
 Title    Investigation of the C-Cl Bonds in Trichloroacrylic Acid, Cl 2 C = CClCOOH, by Single Crystal Zeeman Split NQR  
 Abstract    The 35 C1 NQR spectrum of trichloroacrylic acid, C1 2 C = CC1COOH, was studied by single crystal Zeeman NQR spectroscopy at 303 K (high temperature phase I) and at 275 K (low temperature phase II). At 303 K for the = CC1 2 group chlorines it was found eQ<P zz h~ l (35 Cl (i)) = 76.179 MHz, r\ (35 C1) = 0.1597; e 0 <f>zz h ~ 1 (35 C1 (3 >) = 74.693 MHz, r\ (35 C1) = 0.1868 and for the -CC1C -group chlorine eQ<f> zz /i" r (35 Cl (1)) = 75.145 MHz, rj (35 C1) = 0.1568. The difference in the electric field gradients at the stereochemically inequivalent chlorines Cl (2) and Cl (3) is rather large. The asymme-try parameter rj (35 C1 (1)) shows an unusual temperature dependence which probably originates from the change of the hydrogen dynamics and position within the dimeric H-bonded unit (Cl 2 C = CClCOOH) 2 during the phase transition. 
  Reference    Z. Naturforsch. 45a, 243—248 (1990); received August 21 1989 
  Published    1990 
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 Identifier    ZNA-1990-45a-0243 
 Volume    45 
38Author    Stefanie Brummer, Norbert Weiden, Alarich WeissRequires cookie*
 Title    Single Crystal 35 C1 NQR of 2,3,4,4-Tetrachloro-l-oxo-l,4-dihydronaphthaline and of 2,2,3,4-Tetr achloro-1 -oxo-1,2-dihy dronaphthaline  
 Abstract    2,3,4,4-Tetrachloro-l-oxo-l,4-dihydronaphthaline, ß-TKN, crystallizes in the orthorhombic space group D^-Pnma with Z = 4, and the 35 C1 NQR spectrum consists of three lines with an intensity ratio of 2:1:1. The crystal structure of 2,2,3,4-tetrachloro-l-oxo-l,2-dihydronaphthaline, a-TKN, is described in literature as belonging to the polar space group C^-P^ with Z = 2. In contradiction to the reported space group and Z, we observed a three line 35 C1 NQR spectrum with an intensity ratio of 2:1:1. Therefore, the crystal structure of a-TKN was redetermined at 7 = 296 K: space group C^ h -P2 1 /m, Z = 2, a = 888.4 (2) pm, b = 692.3 (2) pm, c = 869.6 (2) pm, >3 = 91.483 (5)°. The nuclear quadrupole coupling tensors have been investigated using a 4n Zeeman NQR goniometer and FT NQR for tracing the zero splitting cones. According to the crystal structure of ß-TKN, two symmetry related zero splitting cones have been found for Cl (2) , two for Cl (3) , and four for Cl (4) (7=297 K). From the single crystal Zeeman split NQR measurements of a-TKN one zero splitting cone has been found for Cl <3) , one for Cl <4) , and two for CI (2) (7=290 K). The asymmetry parameters t] and the direction cosines of the principal axes <P XX , and & :z of the nuclear quadrupole coupling tensors have been determined. The results are: CI" 1 , v (35 C1 0)), e 2 Qqh-1 (35 C1 0)), rj (35 C1 0)) for ß-TKN (at 7=297 K): Cl. By comparing the crystal structures and the 35 C1 NQR results, the C-Cl bonds in the title compounds are discussed. 
  Reference    Z. Naturforsch. 45a, 249—258 (1990); received October 3 1989 
  Published    1990 
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 Identifier    ZNA-1990-45a-0249 
 Volume    45 
39Author    Stefanie Brummer, Ulrich Sohling, Alarich WeissRequires cookie*
 Title    C1 NQR, Crystal Structure, and Pyroelectricity of 2,3-Dichloro-l,4-naphthoquinone  
 Abstract    The 35 C1 NQR spectra of the two phases (phases I and II) of 2,3-dichloro-l,4-naphthoquinone were studied from 77 to 394 K. The crystal structure determination of the triclinic phase (phase I) was refined by single crystal X-ray diffraction. Phase I crystallizes in the space group C/-P1. The unit cell (Z = 4) has the dimensions a = 1614.3(4) pm, 6 = 828.1 (3) pm, c = 733.2(3) pm, a = 67.02(l)°, /? = 82.55(1)°, y = 89.77(1)°. In the temperature range 439^ 7^,,/K ^447 a unidirectional phase transition I —> II is observed. Phase II is orthorhombic, space group C2 V -Pb2 1 a. The bond distances d<c-cn and the 35 C1 NQR frequencies correlate quite well according to the theory: v(35 Cl) ~ (rf(c-ci)) 3 -The multiplicity of the 35 C1 NQR spectra is discussed. Pyroelectricity studies on phase II are reported. The pyroelectric coefficient depends little on the temperature, 8.3 ^ p x /\iC m~ 2 K~ 1 ^ 10.7 in 103 ^ T/K ^ 343. 
  Reference    Z. Naturforsch. 45a, 259—267 (1990); received August 7 1989 
  Published    1990 
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 Identifier    ZNA-1990-45a-0259 
 Volume    45 
40Author    Donghoon Lee, S. J. Gravina, P. J. BrayRequires cookie*
 Title    NQR Studies of Atomic Arrangements and Chemical Bonding in Glasses* 3  
 Abstract    A very high sensitivity continuous wave NQR spectrometer was developed to detect pure NQR transitions at low frequencies (down to 200 kHz). A signal-to-noise ratio of more than 100 to 1 has been achieved at about 1.36 MHz for crystalline B 2 0 3 . Two large n B responses have been found in vitreous B 2 0 3 (NMR detected only one site) with linewidths of less than 30 kHz. 27 A1 NQR spectra were obtained for OC-A1203 (Corundum), the mineral andalusite (a form of A1203 • Si0 2), and a glass having the composition of anorthite (CaO • A1203 • 2Si0 2). 
  Reference    Z. Naturforsch. 45a, 268—272 (1990); received September 81989 in revised form November 9 1989 
  Published    1990 
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 Identifier    ZNA-1990-45a-0268 
 Volume    45 
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