Bond-Shift Rearrangement in Solid Li3P7(Monoglyme)3: A P MAS NMR Study

The ³¹P MAS NMR spectrum of solid Li₃P₇(monoglyme)₃ has been reinvestigated over a wide temperature range (−70 to +77°C) and under conditions of better resolution (Larmor frequency of 162 MHz and spinning rate of 30 kHz) than previously measured (121 MHz and 13 kHz). At low temperatures three spinning sideband (ssb) manifolds are observed: a singlet (centered at −45 ppm relative to 85% H₃PO₄) due to the apical atom (A) of the P₇-cage trianion; a 1 : 1 : 1 triplet (at −110, −117, and −124.5 ppm) due to the negatively charged equatorial (E) atoms, and a one to two doublet (at −161 and −168.5 ppm) due to the basal (B) atoms. These results are consistent with the P₇ cage having nearly, but not perfect, C_3v symmetry. The compound appears to be well ordered in the solid state with very little structural dispersity. On heating, the NMR lines broaden and eventually coalesce into a single ssb manifold. This behavior is ascribed to bond-shift rearrangement similar to the Cope rearrangement in bullvalene. A MAS 2D exchange experiment and a quantitative analysis of the 1D NMR lineshapes indicate that, unlike in solution where the rearrangement involves a single bond shift at a time, in the solid the process involves a succession of two bond shifts: The first leads to an intermediate species in which the rearranged P₇ cage is inverted, while in the subsequent step a second bond shift takes place that also restores the original orientation of the cage in the lattice. The overall effect of the double bond shift is equivalent to cyclic permutation of the phosphorus atoms within the five member rings of the P₇-cage. The quantitative analysis of the dynamic lineshapes shows that this cyclic permutation proceeds at a different rate in one ring (k_d¹) than in the other two (k_d^2,3). The kinetic parameters for these processes are E_a¹=18.7 kJ/mol, E_a^2,3=58.0 kJ/mol, k_d¹(17°C)=k_d^2,3(17°C)=10⁴ s⁻¹. No indications for independent threefold molecular jumps of the P₇ cage were found.     

Cobalt-59 NMR and X-ray diffraction studies of hydrated and dehydrated (+/-)-tris(ethylenediamine) cobalt(III) chloride

Cobalt-59 NMR experiments have been carried out on single-crystal and polycrystalline (powder) samples of (+/-)-tris(ethylenediamine)cobalt(III) chloride trihydrate, (+/-)-[Co(en)(3)]Cl(3) x 3H(2)O, and of its dehydrate. In addition, the X-ray crystal structure of the dehydrated sample has been determined. X-ray diffraction measurements confirm a long-held assumption that dehydration has only minor effects on the structure of the [Co(en)(3)](3+) cation. Nevertheless, these small differences have a detectable effect on the 59Co nuclear magnetic resonance properties of these compounds; in particular, the nuclear quadrupole coupling constant, C(Q). Straightforward identification of the c-axis for large single crystals of (+/-)-[Co(en)(3)]Cl(3).3H(2)O and of its dehydrate allowed us to obtain single-crystal 59 Co NMR data by orienting the crystals in an MAS rotor. Data collected on single crystals and polycrystalline samples indicate that C(Q)=-3.05+/-0.05 and -2.80+/-0.05 MHz for the hydrated and dehydrated samples, respectively; the signs have been assigned on the basis of a point charge model. The chemical shift tensor principal components were also determined: for the hydrated sample, delta(perpendicular)=7281+/-2 ppm, delta(parallel)=7004+/-4 ppm and delta(iso)=7189 ppm; for the dehydrated sample, delta(perpendicular)=7288+/-2 ppm, delta(parallel)=7008+/-4 ppm and delta(iso)=7195 ppm. The electric field gradient and chemical shift tensors are axially symmetric, as required by crystal symmetry.     

Theoretical study of two-dimensional COSY experiments for S = 7/2 spins: application to (59)Co in the tetrahedral cluster HFeCo(3)(CO)(11)PPh(2)H

The first investigation and analysis of (59)Co 2D NMR homonuclear chemical shift correlation spectra are reported for the tetrahedral mixed-metal cluster HFeCo(3)(CO)(11)PPh(2)H. For this cluster in solution, the (59)Co 2D COSY and DQF COSY NMR spectra prove the existence of a scalar coupling between (59)Co nuclei. In order to obtain a value of this coupling, the 2D COSY and DQF COSY NMR spectra for a three-spin 7/2 AX(2) system have been simulated by numerical density matrix calculations. The comparison between experimental and theoretical 2D NMR spectra gives a spin-coupling constant |(1)J((59)Co - (59)Co)| = (115 +/- 20) Hz for this cluster. Experimental measurements of T(1) and of the line widths for cobalt 59 as well as theoretical (59)Co 1D NMR spectra are reported and support our findings.     

59Co chemical shift anisotropy and quadrupole coupling for K3Co(CN)6 from MQMAS and MAS NMR spectroscopy

59Co triple-quantum (3Q) MAS and single-pulse MAS NMR spectra of K3Co(CN)6 have been obtained at 14.1 T and used in a comparison of these methods for determination of small chemical shift anisotropies for spin I = 7/2 nuclei. From the 3QMAS NMR spectrum a spinning sideband manifold in the isotropic dimension with high resolution is reconstructed from the intensities of all spinning sidebands in the 3QMAS spectrum. The chemical shift anisotropy (CSA) parameters determined from this spectrum are compared with those obtained from MAS NMR spectra of (i) the complete manifold of spinning sidebands for the central and satellite transitions and of (ii) the second-order quadrupolar lineshapes for the centerband and spinning sidebands from the central transition. A good agreement between the three data sets, all of high precision, is obtained for the shift anisotropy (delta(sigma) = delta(iso) - delta(zz)) whereas minor deviations are observed for the CSA asymmetry parameter (eta(sigma)). The temperature dependence of the isotropic 59Co chemical shift has been studied over a temperature range from -28 to +76 degrees C. A linear and positive temperature dependence of 0.97 ppm/degree C is observed.     

Determination of the 17O NMR tensors in potassium hydrogen dibenzoate: a salt containing a short O...H...O hydrogen bond

Solid-state 17O NMR spectra were obtained at 4.70, 11.75 and 19.60T for potassium hydrogen [17O(4)]dibenzoate (PHB) under both magic-angle spinning and stationary conditions. Spectral analyses yielded both the magnitude and orientation of the 17O chemical shift (CS) tensor and the electric field gradient (EFG) tensor for each of the two chemically distinct oxygen sites in PHB. For the oxygen site that is not involved in hydrogen bonding, the experimental 17O NMR tensors are: delta(iso)=287+/-2 ppm, delta(11)=470+/-5 ppm, delta(22)=380+/-5 ppm, delta(33)=10+/-5 ppm, C(Q)=8.30+/-0.02 MHz, eta(Q)=0.23+/-0.05, alpha=0+/-5 degrees, beta=90+/-5 degrees, and gamma=30+/-5 degrees. For the oxygen site in the short O...H...O hydrogen bond, the experimental 17O NMR tensors are: delta(iso)=213+/-2 ppm, delta(11)=370+/-5 ppm, delta(22)=190+/-5 ppm, delta(33)=80+/-5 ppm, C(Q)=5.90+/-0.02 MHz, eta(Q)=0.55+/-0.05, alpha=5+/-5 degrees, beta=90+/-5 degrees, and gamma=90+/-5 degrees. Extensive quantum mechanical calculations at both restricted Hartree-Fock and density functional theory levels were performed to investigate the effects of an effectively symmetrical O...H...O hydrogen bond on 17O CS and EFG tensors.     

巴基球C60内嵌原子(Li,Na,K,Rb,Cs;F,Cl,Br,I)的稳定存在位置及其复合物的几何与电子结构

本文用量子化学EHMO/ASED方法对巴基球C60内嵌原子(A=Li,Na,K,Rb,Cs;F,Cl,Br,I)进行了计算。结果表明除Li、Na外,其它元素当置于C60笼中心附近时,复合物能量最低,最稳定;对于内嵌Li、Na原子的巴基球(Li@C60)及(Na@C60),当Li、Na位于围绕中心的一个球壳层(r～1.5A)内时最稳定。     

The (1)(3)Pi Electronic State of LaF

Rotational studies of bands of the infrared systems (1)(3)Pi-->(1)(3)Delta and (1)(3)Pi(1)-->X(1)Sigma(+) of lanthanum monofluoride were carried out with the aim of characterizing the (1)(3)Pi state, assuming the previous representations of X(1)Sigma(+) and (1)(3)Delta (1-3). The vibrational levels of (1)(3)Pi involved in the analyzed transitions were v=0, 1, 2 of the Omega=0 component, v=0, 1 of the Omega=1 component, and v=0 of the Omega=2 component. Perturbations were observed in both systems which were ascribed to spin-uncoupling interactions between (1)(3)Pi(2)(v=0) and (1)(3)Pi(1)(v=1) levels. A 9x9 matrix representation at equilibrium of the complex of interacting levels (v=0, 1, 2) was constructed, each diagonal v-block corresponding to a triplet model of the rovibrational (3)Pi Hamiltonian. The wavenumbers of some 1910 lines in the two systems were simultaneously fitted (rms error of the fit of about 0.0053 cm(-1)), thus yielding a consistent set of accurate spectroscopic constants for the (1)(3)Pi state; the spin-uncoupling interaction parameter was determined as B(Pi)(0, 1)=0.010917(13) cm(-1). Copyright 2001 Academic Press.     

Interplay between Fe 3d and Ce 4f magnetism and Kondo interaction in CeFeAs(1-x)P(x)O probed by 75As and 31P NMR

A detailed (31)P (I = 1/2) and (75)As (I = 3/2) NMR study on polycrystalline CeFeAs(1-x)P(x)O alloys is presented. The magnetism of CeFeAsO changes drastically upon P substitution on the As site. CeFePO is a heavy fermion system without long-range order whereas CeFeAsO exhibits an Fe 3d SDW type of ordering accompanied by a structural transition from tetragonal (TT) to orthorhombic (OT) structure. Furthermore, Ce 4f(1) orders antiferromagnetically (AFM) at low temperature. At the critical concentration where the Fe magnetism is diminished the Ce-Ce interaction changes to a ferromagnetic (FM) type of ordering. Three representative samples of the CeFeAs(1-x)P(x)O (x = 0.05, 0.3 and 0.9) series are systematically investigated. (1) For the x = 0.05 alloy a drastic change of the linewidth at 130 K indicates the AFM-SDW type of ordering of Fe and the structural change from the TT to the OT phase. The linewidth roughly measures the internal field in the ordered state and the transition is most likely first order. The small and nearly constant shift from (31)P and (75)As NMR suggests the presence of competing hyperfine interactions between the nuclear spins and the 4f and 3d ions of Ce and Fe. (2) For the x = 0.3 alloy, the evolution of the Fe-SDW type of order takes place at around 70 K corroborating the results of bulk measurement and μSR. Here we found evidence for phase separation of paramagnetic and magnetic SDW phases. (3) In contrast to the heavy fermion CeFePO for the x = 0.9 alloy a phase transition is found at 2 K. The field-dependent NMR shift gives evidence of FM ordering. Above the ordering the spin-lattice relaxation rate (31)(1/T(1)) shows unconventional, non-Korringa-like behaviour which indicates a complex interplay of Kondo and FM fluctuations.     

The H(2)(18)O solvent-induced isotope shift in (19)F NMR

The H(2)(16)O/H(2)(18)O solvent-induced isotope shifts ((18)O SIIS) of the (19)F NMR signals of a number of fluorine compounds have been measured. These isotope shifts are observed to be upfield, downfield, or zero, depending on the specific compound and the precise solution conditions. At 25 degrees C and with an (18)O enrichment of 86%, the (18)O SIIS of several fluorinated amino acids were in the range of 0.0014-0.0018 ppm downfield. 5-Fluorouridine displays a significantly wider range of (18)O SIIS values. A 5-fluorouridine-labeled 16-mer RNA also displayed observable (18)O SIIS values, but the characteristics of these were significantly modified from those of free 5-fluorouridine. The experimental observations are consistent with the (18)O SIIS being composed of upfield and downfield components, with the relative contributions of these determining the size and direction of the overall isotope shift. This is discussed in terms of a combination of van der Waals interactions between the fluorine atom and the solvent, electrical and hydrogen bonding effects, and the perturbations to these due to (18)O substitution in the solvent water. This isotope effect promises to be a highly useful tool in a range of (19)F NMR studies.     

Determination of NMR interaction parameters from double rotation NMR

It is shown that the anisotropic NMR parameters for half-integer quadrupolar nuclei can be determined using double rotation (DOR) NMR at a single magnetic field with comparable accuracy to multi-field static and MAS experiments. The (17)O nuclei in isotopically enriched l-alanine and OPPh(3) are used as illustrations. The anisotropic NMR parameters are obtained from spectral simulation of the DOR spinning sideband intensities using a computer program written with the GAMMA spin-simulation libraries. Contributions due to the quadrupolar interaction, chemical shift anisotropy, dipolar coupling and J coupling are included in the simulations. In l-alanine the oxygen chemical shift span is 455 +/- 20 ppm and 350 +/- 20 ppm for the O1 and O2 sites, respectively, and the Euler angles are determined to an accuracy of +/- 5-10 degrees . For cases where effects due to heteronuclear J and dipolar coupling are observed, it is possible to determine the angle between the internuclear vector and the principal axis of the electric field gradient (EFG). Thus, the orientation of the major components of both the EFG and chemical shift tensors (i.e., V(33) and delta(33)) in the molecular frame may be obtained from the relative intensity of the split DOR peaks. For OPPh(3) the principal axis of the (17)O EFG is found to be close to the O-P bond, and the (17)O-(31)P one-bond J coupling ((1)J(OP)=161 +/- 2 Hz) is determined to a much higher accuracy than previously.     

Theoretical study on the reactions of CH3NHNH2 with ground state O(3P) atom and excited state O(1D) atom

The reaction mechanisms of methylhydrazine (CH₃NHNH₂) with O(³P) and O(¹D) atoms have been explored theoretically at the MPW1K/6-311+G(d,p), MP2/6-311+G(d,p), MCG3-MPWPW91 (single-point), and CCSD(T)/cc-pVTZ (single-point) levels. The triplet potential energy surface for the reaction of CH₃NHNH₂ with O(³P) includes seven stable isomers and eight transition states. When the O(³P) atom approaches CH₃NHNH₂, the heavy atoms, namely N and C atoms, are the favourable combining points. O(³P) atom attacking the middle-N atom in CH₃NHNH₂ results in the formation of an energy-rich isomer (CH₃NHONH₂) followed by migration of O(³P) atom from middle-N atom to middle-H atom leading to the product P6 (CH₃NNH₂+OH), which is one of the most favourable routes. The estimated major product CH₃NNH₂ is consistent with the experimental measurements. Reaction of O(¹D) + CH₃NHNH₂ presents different features as compared with O(³P) + CH₃NHNH₂. O(¹D) atom will first insert into C–H2, N1–H4, and N2–H5 bonds barrierlessly to form the three adducts, respectively. There are two most favourable paths for O(¹D) + CH₃NHNH₂. One is that the C–N bond cleavage accompanied by a concerted H shift from O atom to N atom (mid-N) leads to the product P_I (CH₂O + NH₂NH₂), and the other is that the N–N bond rupture along with a concerted H shift from O to N (end-N) forms P_IV (CH₃NH₂ + HNO). The similarities and discrepancies between two reactions are discussed.     

Solid-state 25Mg QCPMG NMR of bis(cyclopentadienyl)magnesium

Application of the "quadrupolar Carr-Purcell Meiboom-Gill" (QCPMG) sequence permits the first natural abundance solid-state 25Mg NMR study of an organometallic magnesium compound, bis(cyclopentadienyl)magnesium. Analytical and numerical simulations of both static and magic-angle spinning QCPMG NMR spectra beget an axially symmetric 25Mg electric field gradient (EFG) tensor (quadrupolar asymmetry parameter, eta(Q)=0.01(1)) with a nuclear quadrupole coupling constant of C(Q)=5.80(5)MHz. Restricted Hartree-Fock and hybrid density functional theory (B3LYP) calculations are in good agreement with experimental EFG values and predict a chemical shielding anisotropy of about 40-50 ppm, which we attempt to elucidate by numerical simulations. The parameters and orientation of the 25Mg EFG tensor are rationalized from examination of the crystal structure and molecular symmetry. The NMR properties of the cyclopentadienyl rings are examined by 13C[1H] CPMAS NMR, RHF and hybrid-DFT (B3LYP) calculations, and simulations of the effects of chemical exchange on the 13C powder pattern.     

Stability of (3)He(2)(4)He(n) and (3)He(3)(4)He(n) L=0 clusters

We have studied the stability of mixed (3)He/(4)He clusters in L=0 states by the diffusion Monte Carlo method, employing the Tang-Toennies-Yiu He-He potential. The clusters (3)He(4)He(N) and (3)He(2)(4)He(N) are stable for N>1. The lighter atoms tend to move to the surface of the cluster. The minimum number of 4He atoms able to bind three 3He atoms in a L=0 state is nine. Two of three fermionic helium atoms stay on the surface, while the third one penetrates into the cluster.     

Observation of the Hadronic transitions chi(b1,2)(2P)-->omegaUpsilon(1S)

The CLEO Collaboration has made the first observations of hadronic transitions among bottomonium (bbmacr;) states other than the dipion transitions among Upsilon(nS) states. In our study of Upsilon(3S) decays, we find a significant signal for Upsilon(3S)-->gammaomegaUpsilon(1S) that is consistent with radiative decays Upsilon(3S)-->gammachi(b1,2)(2P), followed by chi(b1,2)(2P)-->omegaUpsilon(1S). The branching ratios we obtain are B[chi(b1)(2P)-->omegaUpsilon(1S)]=(1.63(+0.35+0.16)(-0.31-0.15))% and B[chi(b2)(2P)-->omegaUpsilon(1S)]=(1.10(+0.32+0.11)(-0.28-0.10))%, in which the first error is statistical and the second is systematic.     

Measurement of absolute cross sections for excitation of the 3s(2)3p(5) 2P(o)(3/2)- 3s(2)3p(5) 2P(o)(1/2) fine-structure transition in Fe9+

Experimental cross sections are reported for the 3s(2)3p(5) 2P(o)(3/2)- 3s(2)3p(5) 2P(o)(1/2) transition in Fe9+ located at 1.945 eV. The center-of-mass interaction energies are in the range of 1.72 eV (below threshold) through threshold, to 5.6 eV (2.9 x threshold). Data are compared with results of a 49-state Breit-Pauli R-matrix theory. The experiment detects structures at 3.5 and 4.6 eV corresponding to enhancement of the direct excitation via many narrow, closely spaced resonances about these energies calculated by the theory. Iron is present in practically every astrophysical object, as well as being an impurity in fusion plasmas. Present data are the first electron-energy-loss measurements on a highly charged iron ion.     

The Near-Infrared (3)Phi --> (1)(3)Delta Transition of LaF

Rotational analyses of 32 subbands of the near-infrared (3)Phi --> (1)(3)Delta system of LaF have been carried out, involving the levels v = 0-7 of the two states. The three subsystems were first treated as separate singlet systems, directly at equilibrium. Perturbations were revealed in the lower state, ascribed to spin-uncoupling interactions between (1)(3)Delta(3)(v) and (1)(3)Delta(2)(v + 1) levels. A 21 x 21 matrix representation at equilibrium of the complex of interacting levels (v = 0-6) was then constructed, each diagonal v-block corresponding to a triplet model of the rovibrational (3)Delta Hamiltonian. The observed perturbations were completely reduced in the harmonic oscillator approximation with an experimental value of the interaction parameter B(Delta)(0,1) = 0.01322(2) cm(-1). The wavenumbers of some 4500 lines of the system were fitted with an rms error of about 0.005 cm(-1). (Line lists are available in electronic form via http://www-obs.univ-lyon1.fr/~ABernard/index.html.) Copyright 2000 Academic Press.     

Natural abundance (17)O NMR spectroscopy of rat brain in vivo

Oxygen is an abundant element that is present in almost all biologically relevant molecules. NMR observation of oxygen has been relatively limited since the NMR-active isotope, oxygen-17, is only present at a 0.037% natural abundance. Furthermore, as a spin 5/2 nucleus oxygen-17 has a moderately strong quadrupole moment which leads to fairly broad resonances (T(2)=1-4 ms). However, the similarly short T(1) relaxation constants allow substantial signal averaging, whereas the large chemical shift range (>300 ppm) improves the spectral resolution of (17)O NMR. Here it is shown that high-quality, natural abundance (17)O NMR spectra can be obtained from rat brain in vivo at 11.74 T. The chemical shifts and line widths of more than 20 oxygen-containing metabolites are established and the sensitivity and potential for (17)O-enriched NMR studies are estimated.     

Hyperfine splitting,isotope shift,and level energy of the 3S states of (6,7)Li

We study the 2S-3S transition of (6,7)Li by high-precision laser spectroscopy using two-photon Doppler-free excitation and photoionization detection. Interferometric cross referencing to metrologic Rb 3S-5D two-photon transitions allowed measurement of the transition isotope shift and hyperfine splitting in the 3S state with precision at the 30 kHz level. The results are IS=11 453.734(30) MHz, A(3S)(6Li)=35.263(15) MHz, and A(3S)(7Li)=93.106(11) MHz. Combined with recent theoretical work, the isotope shift yields a new value for the change in squared nuclear charge radii DeltaR(2)=0.47(5) fm(2). This is compared with other work and some existing discrepancies are resolved.     

Measurement of the B(e2) of (7)(lambda)Li and shrinkage of the hypernuclear size

We report on the first measurement of a hypernuclear gamma-transition probability. gamma rays emitted in the E2(5/2(+)-->1/2(+)) transition of (7)(Lambda)Li were detected by a large-acceptance germanium detector array (Hyperball), and the lifetime of the parent state ( 5/2(+)) was determined by the Doppler shift attenuation method. The obtained result, 5.8(+0.9)(-0.7)+/-0.7 ps, was then converted into the reduced transition probability [ B(E2)] to be B(E2;5/2(+)-->1/2(+)) = 3.6+/-0.5(+0.5)(-0.4) e(2) fm(4). Compared with the B(E2) of the corresponding E2(3(+)-->1(+)) transition in the 6Li nucleus, our result gives evidence that the size of the 6Li core in (7)(Lambda)Li is smaller than the 6Li nucleus in the free space.