Pulsed-laser photolysis of Mn2(CO)10: A time-resolved fluorescence study

Mn₂(CO)₁₀ was photolysed in the gas phase by the XeCl-excimer laser with fluence in the range 25–300 mJ/cm² and a dye laser. The UV/VIS emission of the products was probed on a nanosecond time scale. The emission from excited states of metal atoms was detected only. The Mn atoms are predominantly formed in their ground statea ⁶ S _{2 1/2}. The absorption of one photon and the subsequent relaxation process leads to the formation ofz ⁶ P _J ⁰ (J = 11/2, 21/2, 31/2) states and emission of photons at a wavelength of 403 nm. The formation of the excited statese ⁸ D _{5 1/2},z ⁶ F _{4 1/2} ⁰ ande ⁶ D _{4 1/2} and the subsequent emission observed at wavelengths of 357, 383 and 446 nm requires the absorption of two photons by the ground-state Mn atoms. In addition, transition from thea ⁶ D _j (J = 11/2, 21/2) lower states were observed in the wavelength-resolved Laser-Induced Fluorescence (LIF) spectra.     

Steady state signal in the limit of weak optical pumping with D1 or D2 line

The simplified rate equations for electronic polarization of alkali atoms in the hyperfine ground states are shown for circularly polarizedD ₁ andD ₂ lines in the limit of weak pumping. The rate equations include effects due to collisional and spin exchange relaxation of atoms in the ground state. Analytical forms of the repopulation pumping terms are shown assuming the standardJ-randomization model for relaxation of alkali atoms in resonant² P _J states and neglecting energy transfer. Analyses of the analytical steady state solutions have been performed to determine the conditions at which the longitudinal electronic orientation of alkali atoms 〈S _z〉 and the orientation of atoms in hyperfine sublevels 〈S _z〉 _f pass through zero.     

Measurement of Dipolar Couplings for Methylene and Methyl Sites in Weakly Oriented Macromolecules and Their Use in Structure Determination

A simple and effective method is described for simultaneously measuring dipolar couplings for methine, methylene, and methyl groups in weakly oriented macromolecules. The method is aJ-modulated 3D version of the well-known [¹H-¹³C] CT-HSQC experiment, from which theJand dipolar information are most accurately extracted by using time-domain fitting in the third, constant-time dimension. For CH₂-sites, the method generally yields only the sum of the two individual¹³C-¹H couplings. Structure calculations are carried out by minimizing the deviation between the measured sum, and the sum predicted for each methylene on the basis of the structure. For rapidly spinning methyl groups the dipolar contribution to the splitting of the outer¹³C quartet components can be used directly to constrain the orientation of the C-CH₃bond. Measured sidechain dipolar couplings are in good agreement with an ensemble of NMR structures calculated without use of these couplings.     

Determination of Backbone Angle ψ in Proteins Using a TROSY-Based α/β-HN(CO)CA-J Experiment

Transverse relaxation-optimized NMR experiment (TROSY) for the measurement of three-bond scalar coupling constant between ¹H^α_i−1 and ¹⁵N_i defining the dihedral angle ψ is described. The triple-spin-state-selective experiment allows measurement of ³J_H^αN from ¹³C^α, ¹⁵N, and ¹H^N correlation spectra H₂O with minimum resonance overlap. Transverse relaxation of ¹³C^α spin is minimized by using spin-state-selective filtering and by acquiring a signal longer in ¹⁵N-dimension in a manner of semi-constant-time TROSY evolution. The ³J_H^αN values obtained with the proposed α/β-HN(CO)CA-J TROSY scheme are in good agreement with the values measured earlier from ubiquitin in D₂O using the HCACO[N] experiment.     

Measurement ofJand Dipolar Couplings from Simplified Two-Dimensional NMR Spectra

Simple procedures are described for recording complementary in-phase and antiphaseJ-coupled NMR spectra. The sum and difference of these spectra contain only the upfield and the downfield components of a doublet, making it possible to measure theJsplitting directly from these combinations without an increase in resonance overlap relative to the decoupled spectrum. The approach is demonstrated for measurement of¹J_NHsplittings and²J_HNC′splittings in oriented and isotropic ubiquitin. Dipolar couplings obtained from differences in the splittings measured in the oriented and isotropic phases are in excellent agreement with dipolar couplings obtained from direct measurement of the splitting or from a conventional E.COSY-type measurement.     

DNA Duplex Dynamics: NMR Relaxation Studies of a Decamer with UniformlyC-Labeled Purine Nucleotides

Dynamics in a DNA decamer duplex,d(CATTTGCATC) ·d(GATGCAAATG), were investigated via a detailed¹³C NMR relaxation study. Every 2′-deoxyadenosine and 2′-deoxyguanidine was chemically enriched with 15%¹³C and 98%¹⁵N isotopes. Six nuclear relaxation parameters [R(¹³C_z),R(¹H_z),R(2¹H_z¹³C_z),R(¹³C_x),R(2¹H_z¹³C_x) and steady-state¹³C{¹H} NOE] were measured at 600 MHz and three were measured at 500 MHz (¹H frequency) for the CH spin systems of sugar 1′, 3′, and 4′ as well as base 8 and 2 positions. A dependence of relaxation parameter values on chemical position was clearly observed; however, no sequence-specific variation was readily evident within our experimental error of ∼5–10%, except for 3′ and 5′ termini. It was demonstrated that the random 15%¹³C enrichment effectively suppressed both scalar and dipolar contributions of the neighboring carbons and protons on the relaxation parameters. To analyze dynamics via all observed relaxation parameters, full spectral density mapping (1992, J. W. Peng and G. Wagner,J. Magn. Reson.98, 308) and the “model-free” approach (1982, Lipari and Szabo,J. Am. Chem. Soc.104, 4546) were applied complementarily. A linear correlation between three spectral density values,J(ω_C),J(ω_H− ω_C), andJ(ω_H+ ω_C) was observed in plots containing all measured values, but not for the other spectral density terms includingJ(0). These linear correlations reflect the effect of overall motion and similar internal motions for each CH vector in the decamer. The correlations yielded two correlation times, 3–4 ns and 10–200 ps. One value, 3–4 ns, corresponds to the value of 3.3 ns obtained for the overall isotropic tumbling correlation time determined from analysis of¹³C T1/T2 ratios. The possibility of overall anisotropic tumbling was examined, but statistical analysis showed no advantage over the assumption of simple isotropic tumbling. Lack of correlations entailingJ(0) implies that a relatively slow chemical exchange contributes to yielding of effectiveJ_eff(0) values. Based on spectral density mapping and the T1/T2 ratio analysis, three basic assumptions were initially employed (and subsequently justified) for the model-free calculation: isotropic overall tumbling, one internal motion, and the presence of chemical exchange terms. Except for terminal residues, the order parameterS²and the corresponding fast internal motion correlation time were determined to be about 0.8 ± 0.1 and 20 ± 20 ps, respectively, for the various CH vectors. Only a few differences were observed between or within sugars and bases. The internal motion is very fast (ps–ns time scale) and its amplitude restricted; e.g., assuming a simple wobble-in-a-cone model, the internal motion is restricted to an angular amplitude of ±22.5° for each of the 1′, 3′, 4′, 2, and 8 positions in the purine nucleotides in the entire duplex.     

Measurement of the transverse Doppler shift using a stored relativistic7Li+ ion beam

We have performed for the first time precision spectroscopy on a coasting fast⁷Li⁺ ion beam in a storage ring. The ion beam moving with 6.4% speed of light was first electron cooled and then merged with two counterpropagating laser beams acting on two different hyperfine transitions sharing a common upper level (λ-system). One laser was frequency locked to thea ₃ ¹²⁷J₂ hfs frequency component established as a secondary frequency standard at 514 nm. The second laser was tuned over theλ-resonance, which was recorded relative to¹²⁷J₂ hfs components. This experiment is sensitive to the time dilation in fast moving frames and will lead to new limits for the verification of special relatively. The present status of the experiment and perspectives in accuracy are discussed.     

P.E.HSQC: a simple experiment for simultaneous and sign-sensitive measurement of (1JCH+DCH) and (2JHH+DHH) couplings

The angular information content of residual dipolar couplings between nuclei of fixed distance makes the accurate and sign-sensitive measurement of (¹J_CH + D_CH) and (²J_HH + D_HH) couplings highly desirable. Experiments published so far are typically highly specialized for the effective measurement of a subset of couplings. The P.E.HSQC presented here, is an E.COSY based experiment which allows the simultaneous measurement of all heteronuclear and homonuclear couplings within CH, CH₂, and CH₃ groups in a single spectrum with the necessary precision and sign information. The simplicity of the approach and the absence of artefacts like phase distortions due to antiphase evolution make it ideally suited for coupling determination of organic molecules at natural abundance.     

Deuteron NMR study of dynamics and order in the columnar phase of a fluorinated discotic liquid crystal

Measurements have been made of deuteron quadrupolar splitting and spin—lattice relaxation times T _1Q and T _1z in the columnar phase of a ring deuterated 1-fluoro-2,3,6,7,10,11-hexahex-yloxytriphenylene (F-HAT6) as a function of temperature and at two different Larmor frequencies. The disc-like molecules are stacked, with only short range positional order, into columns which are arranged on a 2-dimensional hexagonal lattice. To describe small step reorientations of these molecules, a rotational diffusion model which uses a space-fixed frame to diagonalize the molecular diffusion tensor is adopted. The principal diffusion constants in this so called ‘anisotropic viscosity model’ Dα and Dβ are for rotations of a molecule around and perpendicular to the columnar axis, respectively. A global target analysis of the spectral densities J ₁(ω₀) and J ₂(2ω₀) at seven temperatures and two Larmor frequencies in a single minimization procedure was carried out. It was found that Dα Dβ, which is consistent with the picture that the motion towards or away from the local director (i.e., the columnar axis) tends to disrupt the packing of molecules within the column. Furthermore, the activation energies Eαβ and Eβ_a for these motions were found to be 67.7 kJmol^?1 and 56.3kJmol^?1. That these values are higher in comparison with those for HAT6 is interesting, and believed to be a result of a strong lateral dipole in F-HAT6.     

Consequences of the complex character of the internal symmetry in supersymmetric theories

The consequences of the invariance of the superpotential under the complexificationG ^c of the internal symmetry group on the determination of the possible patterns of symmetry and supersymmetry breaking are established in a globally supersymmetric theory. In particular, in the case of global internal symmetry we show that a vacuum associaated to a pointz, whereG _z ^c G _z ^c is always degenerate with a vacuum associated to a pointz, whereG _z ^c =G _z ^c ; all the other degeneracies of the minimum of the potential on an orbit ofG ^c are also determined and shown to be completely removed when the internal symmetry is gauged. The zeroes of theD-term of a supersymmetric gauge theory are characterized as the points of the closed orbits ofG ^c which are at minimum distance from the origin; at these pointsG _z ^c =G _z ^c . It is rigorously proved that the minimum of the potential is zero if the gradient of the superpotential vanishes somewhere. It is also shown that theD-term necessarily vanishes at the minimum of the potential if the direction of spontaneous supersymmetry breaking is invariant byG.Partially supported by the Swiss National Science Foundation and INFN, Sezione di PadovaOn leave of absence from the Department of Physics of the University of Padova, Italy     

In Vivo3D LocalizedC Spectroscopy Using Modified INEPT and DEPT

The 3D localized¹³C spectroscopy methods LINEPT and LODEPT, which are modifications of INEPT and DEPT, are proposed. As long as a¹³C inversion pulse (180-degree pulse) is applied at 1/(4J) before the proton echo time in LINEPT and a¹³C excitation pulse (90-degree pulse) is applied at 1/(2J) before the proton echo time in LODEPT, the proton echo time can be set to any value longer than 1/(2J) in LINEPT and longer than 1/Jin LODEPT. As a result, the proton and the¹³C pulses can be applied separately and these proton pulses can be made slice-selective pulses. These localization features of LINEPT and LODEPT were evaluated using a phantom consisting of a cylinder filled with ethanol placed inside another cylinder filled with oil, and localized ethanol spectra could be obtained.In vivo3D localized¹³C spectra from the brain of a monkey could be obtained using decoupled LINEPT, and glutamate C-4 appeared directly after the administration of glucose C-1, followed by the appearance of glutamate C-2, C-3 and glutamine C-2, C-3, C-4.     

Precision measurement of theg J factors of metastable atomic states of88Sr and138Ba using the atomic beam magnetic resonance method

Theg _J factors of the metastable states³ P ₂ of⁸⁸Sr and³ D ₁,³ D ₂,³ D ₃, and¹ D ₂ of¹³⁸Ba have been measured using the atomic-beam magnetic resonance method. The metastable states were populated by an electric discharge within the atomic-beam source. From the measurements of rf transitions between the Zeeman levels (m _J =+1)?(m _J =?1) we obtained:⁸⁸Sr:g _J (³ P ₂) =1.501124(10)¹³⁸Ba:g _J (³ D ₃)=1.3340823 (10)g _J (³ D′₂)=1.1637406(11)g _J (³ D ₁)=0.4985751(13)g _J (¹ D′₂)=1.003 1449(10). The relativistic and diamagnetic corrections for theg _J factor of the³ P ₂ state of Sr have been calculated. With these and the Schwinger correction included we getg _J (³ P ₂)=1.501119(12).     

The anisotropic 3D Ising model

An expression for the free energy of an (001) oriented domain wall of the anisotropic 3D Ising model is derived. The order--disorder transition takes place when the domain wall free energy vanishes. In the anisotropic limit, where two of the three exchange energies (e.g. J_x and J_y ) are small compared to the third exchange energy (J_z ), the following asymptotically exact equation for the critical temperature is derived, sinh(2J_z /k _B T _c)sinh(2(J_x ?+?J_y )/k _B T _c))?=?1. This expression is in perfect agreement with a mathematically rigorous result (k _B T _c/J_z ?=?2[ln(J_z /(J_x ?+?J_y ))?ln(ln(J_z /(J_x ?+?J_y ))?+?O(1)]^?1) derived earlier by Weng, Griffiths and Fisher (Phys. Rev. 162, 475 (1967)) using an approach that relies on a refinement of the Peierls argument. The constant that was left undetermined in the Weng et al. result is estimated to vary from ～0.84 at ((H_x ?+?H_y )/H_z )?=?10^?2 to ～0.76 at ((H_x ?+?H_y )/H_z )?=?10^?20.     

Spatial averaging and apparent acceleration in inhomogeneous spaces

As an alternative to dark energy that explains the observed acceleration of the universe, it has been suggested that we may be at the center of an inhomogeneous isotropic universe described by a Lemaitre–Tolman–Bondi (LTB) solution of Einstein’s field equations. To test this possibility, it is necessary to solve the null geodesics. In this paper we first give a detailed derivation of a fully analytical set of differential equations for the radial null geodesics as functions of the redshift in LTB models. As an application we use these equaions to show that a positive averaged acceleration a _D obtained in LTB models through spatial averaging can be incompatible with cosmological observations. We provide examples of LTB models with positive a _D which fail to reproduce the observed luminosity distance D _L (z). Since the apparent cosmic acceleration a ^FLRW is obtained from fitting the observed luminosity distance to a FLRW model we conclude that in general a positive a _D in LTB models does not imply a positive a ^FLRW .     

Electron spin resonance and structure of the CO- 2 radical ion

Analysis of the electron spin resonance spectrum shows that CO^? ₂ radical ions are trapped in sodium formate at room temperature after irradiation of the crystal with high energy γ-rays. This radical is bent with an angle of about 134° and has a ² A ₁ ground state. From the experimental values of the ¹³C coupling coefficients and the g values, coefficients are derived for the mixing of atomic orbitals in the half-filled 4a ₁ molecular orbital which appears to be 14 per cent carbon 2s, 66 per cent carbon 2p _z and 11 per cent of each oxygen 2p _z . There is also coupling to the sodium nucleus in an adjacent cation.     

The Ground StateXΣof NaK Revisited

Laser-induced fluorescence (LIF) optical spectra of theD¹Π–X¹Σ⁺system of the NaK molecule have been reinvestigated. In this new analysis, quantum numbers have been assigned to 3000 selected fluorescence lines for a wide range of vibrational and rotational levels (J≤ 149,v′ ≤ 23,v″ ≤ 47). A new set of constants of theX¹Σ state (Dunham-type coefficients) and term values of theD¹Π state have been determined by a weighted least-squares fit of the LIF optical lines of theD–Xsystem, some lines of theC–Xsystem, and microwave spectral data reported recently. Constants forX¹Σ (in cm⁻¹) are as follows: ω_e= 123.993, ω_ex_e= 0.3045,B_e= 0.095229, and α_e= 4.48 × 10⁻⁴. The equilibrium internuclear distance isr_e= 3.49903 Å, very little changed from the microwave value.     

Transition Moments betweenΔg,Πg, andΠuStates of the H2Molecule

Electronic transition moments are computed for dipole transitions between theCandD¹Π_u,IandR¹Π_gandJandS¹Δ_gstates of the hydrogen molecule for internuclear distancesR∈ [1, 15] bohr. The character of the wavefunctions at large internuclear distances is investigated. It is shown that in theDandRstates the asymptotic configurations are strongly mixed forR≤ 15 bohrs. TheSstate has mixed character even atR= 40 bohr.     

Diode Laser Spectroscopy of Trifluoroethylene in the 8.6-μm Region

The two mid-infrared bands of the CF₂=CHF molecule, ν₅centered at 1172.673 cm⁻¹and ν₆+ ν₉at 1155.105 cm⁻¹, were measured on a tunable diode laser spectrometer with a resolution near the Doppler limit. These vibrations ofA′ species give rise toa/bhybrid bands, even though our analysis has pointed out that the intensity of thea-type component is predominant. Most of theJandKstructure has been resolved in different subbranches, and the rovibrational analysis led to the assignment of about 1400 (J≤ 60,K_a≤ 22,K_c≤ 60) and 90 (J≤ 56,K_a≤ 5,K_c≤ 56) lines of the ν₅and ν₆+ ν₉bands, respectively. Using Watson'sA-reduction Hamiltonian in theI^rrepresentation, a set of accurate spectroscopic constants for the upper states has been derived from transitions free of major resonance effects. The rotational structure of the ν₅vibration also exhibits effects of Coriolis perturbation by a state identified as ν₇+ ν₁₁. Parameters for the perturber were determined from the interaction effects near the observed crossings, using a dyad model including first-orderb-Coriolis interaction.