Observing in-phase single-quantum 15N multiplets for NH2/NH3+ groups with two-dimensional heteronuclear correlation spectroscopy

Two-dimensional (2D) F1-(1)H-coupled HSQC experiments provide 3:1:1:3 and 1:0:1 multiplets for AX(3) and AX(2) spin systems, respectively. These multiplets occur because, in addition to the 2S(y)H(z)(a)-->2S(y)H(z)(a) process, the coherence transfers such as 2S(y)H(z)(a)-->2S(y)H(z)(b) occurring in t(1) period provide detectable magnetization during the t(2) period. Here, we present a 2D F1-(1)H-coupled (1)H-(15)N heteronuclear correlation experiment that provides a 1:3:3:1 quartet for AX(3) spin system and a 1:2:1 triplet for AX(2). The experiment is a derivative of 2D HISQC experiment [J. Iwahara, Y.S. Jung, G.M. Clore, Heteronuclear NMR spectroscopy for lysine NH(3) groups in proteins: unique effect of water exchange on (15)N transverse relaxation. J. Am. Chem. Soc. 129 (2007) 2971-2980] and contains a scheme that kills anti-phase single-quantum terms generated in the t(1) period. The purge scheme is essential to observe in-phase single-quantum multiplets. Applications to the NH(2) and NH(3)(+) groups in proteins are demonstrated.     

Fourier Transform Spectroscopy of the A'(1)Pi-X(1)Sigma(+) System of CaO

The A'(1)Pi-X(1)Sigma(+) near-infrared system of CaO was observed for the first time at high resolution using a Fourier transform spectrometer. The A'(1)Pi-X(1)Sigma(+) chemiluminescence was excited in a Ca + N(2)O flame produced in a Broida-type oven. More than 3000 rotational lines, classified into 19 bands involving the A'(1)Pi 0 /= 2) levels with the nearby b(3)Sigma(+) (v-2) levels has been detected. An extended set of A'(1)Pi (v = 0-3) data has been obtained which is suitable for use in a future multistate deperturbation analysis of the a(3)Pi approximately A'(1)Pi approximately b(3)Sigma(+) approximately A(1)Sigma(+) complex of excited states. The new near-infrared spectra of the A'(1)Pi-X(1)Sigma(+) transition of CaO also permits the first direct high-resolution linkage between the orange and green systems and the near-infrared bands. Copyright 2000 Academic Press.     

Fourier Transform Emission Spectroscopy of the Low-Lying Electronic States of NbN

The high-resolution spectrum of NbN has been investigated in emission in the 3000-15 000 cm(-1) region using a Fourier transform spectrometer. The bands were excited in a microwave discharge through a mixture of NbCl(5) vapor, approximately 5 mTorr of N(2), and 3 Torr of He. Numerous bands observed in the near-infrared region have been classified into the following transitions: f(1)Phi-c(1)Gamma, e(1)Pi-a(1)Delta, C(3)Pi(0+)-A(3)Sigma(-)(1), C(3)Pi(0-)-A(3)Sigma(-)(1), C(3)Pi(1)-a(1)Delta, C(3)Pi(1)-A(3)Sigma(-)(0), d(1)Sigma(+)-A(3)Sigma(-)(0), and d(1)Sigma(+)-b(1)Sigma(+). These observations are consistent with the energy level diagram provided by laser excitation and emission spectroscopy [Y. Azuma, G. Huang, M. P. J. Lyne, A. J. Merer, and V. I. Srdanov, J. Chem. Phys. 100, 4138-4155 (1993)]. The missing d(1)Sigma(+) state has been observed for the first time and its spectroscopic parameters are consistent with the theoretical predictions of S. R. Langhoff and W. Bauschlicher, Jr. [J. Mol. Spectrosc. 143, 169-179 (1990)]. Rotational analysis of a number of bands has been obtained and improved spectroscopic parameters have been extracted for the low-lying electronic states. The observation of several vibrational bands with v = 1 has enabled us to determine the vibrational intervals and equilibrium bond lengths for the A(3)Sigma(-)(0), a(1)Delta, b(1)Sigma(+), d(1)Sigma(+), and C(3)Pi(1) states. Copyright 2000 Academic Press.     

Rapid encoding of T(1) with spectral resolution in n-dimensional relaxation correlations

Nuclear magnetic resonance (NMR) T(1) relaxation times have been encoded in the second dimension of two-dimensional relaxation correlation and exchange experiments using a rapid "double-shot"T(1) pulse sequence. This technique also retains chemical shift information (delta) for short T(2)( *) materials. In this way, a spectral dimension can be incorporated into a T(2)-T(1)-delta correlation without an increase in experimental time compared to the conventional, chemically insensitive T(1)-T(2) correlation. Here, the T(2)-T(1)-delta pulse sequence is used to unambiguously identify oil and water fractions in a permeable rock. A novel T(1)-T(1)-(delta) relaxation exchange measurement is also introduced and used to observe diffusive exchange of water in cellulose fibres.     

Theoretical prediction for the ground state of (10 )H e with the method of analytic continuation in the coupling constant

Using the method of analytic continuation in the coupling constant with a (8)He +n+n model, we investigated the ground state of (10)He. In addition to a solution with the two valence neutrons in p states ( [ p(1/2 )p(1/2 )](0+ )), we obtained a solution with the valence neutrons in s states ( [s( 1/2) s(1/2)](0+) ) as the ground state. Experimentally, such a state has not yet been observed. This newly predicted state of (10)He with the main component of [s( 1/2)s (1/2) ](0+) corresponds to the ground state of (11)Li with a halo structure.     

High-Resolution Absorption Spectroscopy of the 3nu(1) and 3nu(1) + nu(3) Bands of Propyne

The 3nu(1) and 3nu(1) + nu(3) bands of propyne have been recorded at Doppler-limited resolution by Fourier transform spectroscopy and intracavity laser absorption spectroscopy, respectively. The two bands show a mostly unperturbed J rotational structure for each individual K subband. However, as a rule the K structure ordering is perturbed in overtone transitions of propyne and different effective parameters associated with each K subband have been determined. From the vibrational energy levels, a value of -6.6 cm(-1) has been obtained for the x(13) cross anharmonicity in perfect agreement with the origins of the nu(1) + nu(3) and 2nu(1) + nu(3) combination bands estimated from the FTIR spectrum. Hot bands from the v(9) = 1 and v(10) = 1 levels associated with the 3nu(1) + nu(3) combination band have been partly rotationally analyzed and the retrieved values of x(39) and x(3,10) are in good agreement with literature values. Finally, the 4nu(1) + nu(9) - nu(9) band centered at 12 636.6 cm(-1) has been recorded by ICLAS. The red shift of this hot band relative to 4nu(1) and the DeltaB(v) value are discussed in relation to the anharmonic interaction between the 4nu(1) and 3nu(1) + nu(3) + nu(5) levels. Copyright 2000 Academic Press.     

Spin gap in the zigzag spin-1/2 chain cuprate Sr(0.9)Ca(0.1)CuO(2)

We report a comparative study of (63)Cu nuclear magnetic resonance spin lattice relaxation rates T(1)(-1) on undoped SrCuO(2) and Ca-doped Sr(0.9)Ca(0.1)CuO(2) spin chain compounds. A temperature independent T(1)(-1) is observed for SrCuO(2) as expected for an S=1/2 Heisenberg chain. Surprisingly, we observe an exponential decrease of T(1)(-1) for T<90 K in the Ca-doped sample evidencing the opening of a spin gap. The data analysis within the J(1)-J(2) Heisenberg model employing density-matrix renormalization group calculations suggests an impurity driven small alternation of the J(2)-exchange coupling as a possible cause of the spin gap.     

Surface reconstructions and phase transitions on the GaAs(111)B surface

The (111)B surface of GaAs has been investigated using scanning tunneling microscopy (STM) and a number of different reconstructions have been found at different surface stoichiometries. In accordance with electron diffraction studies, we find the series (2 × 2), (1 × 1)_LT, ( ) and (1 × 1)_HT with increasing annealing temperature, corresponding to decreasing surface As concentration. The (1 × 1)_LT is of particular interest, since it only occurs in a narrow temperature window between the two more established reconstructions, the (2 × 2) and the ( ). We find the (1 × 1)_LT to take the form of a mixture of the local structures of both the (2 × 2) and ( ) phases, rather than having a distinct structure. This is behaviour consistent with a kinetically limited system, dominated by the supply of As adatoms to the surface, and may be an example of a continuous phase transition. Above the (1 × 1)_LT transition, atomic resolution images of the ( ) surface reveal only a three-fold symmetry of the hexagonal structural units, brought about by inequivalent surface bonding due to the 23.4° rotation of the surface unit cell relative to the substrate. This is responsible for the disorder found in the ( ) reconstruction, since the structure may form in one of two domains. At lower surface As concentration, the (1 × 1)_HT surface adopts a structure combining small domains of a 19.1° structure and random disorder. There is no apparent similarity between the (1 × 1)_LT and (1 × 1)_HT structures, which may be due to our measurements being conducted at room temperature and without an As flux to control the surface As concentration.     

Fourier Transform Infrared Emission Spectroscopy of SeH

The infrared vibration-rotation bands of SeH have been measured in the X(2)Pi ground state using a Fourier transform spectrometer. The bands were observed in a microwave discharge of a mixture of H(2) and Se in the presence of He. The rotational structure of the 1-0, 2-1, 3-2 bands of the X(2)Pi(3/2) spin component and the 1-0 band of X(2)Pi(1/2) spin component has been observed in the 1800-2600 cm(-1) region. The principal ground state molecular constants obtained are omega(e) = 2421.7153(234) cm(-1), omega(e)x(e) = 44.6012(110) cm(-1), omega(e)y(e) = 0.20697(236) cm(-1), B(e) = 7.899187(696) cm(-1), alpha(e) = 0.220749(399) cm(-1), and r(e) = 1.464319(64) ?. This work is the first determination of the equilibrium molecular constants of the X(2)Pi state of SeH. Copyright 2000 Academic Press.     

Constrained modeling for spectroscopic measurement of bi-exponential spin-lattice relaxation of water in vivo

The (1)H NMR water signal from spectroscopic voxels localized in gray matter contains contributions from tissue and cerebral spinal fluid (CSF). A typically weak CSF signal at short echo times makes separating the tissue and CSF spin-lattice relaxation times (T(1)) difficult, often yielding poor precision in a bi-exponential relaxation model. Simulations show that reducing the variables in the T(1) model by using known signal intensity values significantly improves the precision of the T(1) measurement. The method was validated on studies on eight healthy subjects (four males and four females, mean age 21 +/- 2 years) through a total of twenty-four spectroscopic relaxation studies. Each study included both T(1) and spin-spin relaxation (T(2)) experiments. All volumes were localized along the Sylvian fissure using a stimulated echo localization technique with a mixing time of 10 ms. The T(2) experiment consisted of 16 stimulated echo acquisitions ranging from a minimum echo time (TE) of 20 ms to a maximum of 1000 ms, with a repetition time of 12 s. All T(1) experiments consisted of 16 stimulated echo acquisition, using a homospoil saturation recovery technique with a minimum recovery time of 50 ms and a maximum 12 s. The results of the T(2) measurements provided the signal intensity values used in the bi-exponential T(1) model. The mean T(1) values when the signal intensities were constrained by the T(2) results were 1055.4 ms +/- 7.4% for tissue and 5393.5 ms +/- 59% for CSF. When the signal intensities remained free variables in the model, the mean T(1) values were 1085 ms +/- 19.4% and 5038.8 ms +/- 113.0% for tissue and CSF, respectively. The resulting improvement in precision allows the water tissue T(1) value to be included in the spectroscopic characterization of brain tissue.     

Characterization of Electronic Spectra of Rhodium Monohydride and Monodeuteride

Emission spectra of two new electronic transitions of Pb(2) have been measured with a Fourier transform spectrometer in the 5200-8500 cm(-1) range. The emissions were observed from the afterglow of a microwave discharge in a mixture of Pb(x) vapor with hydrogen and argon carrier gas. By comparison with the results of ab initio calculations, the spectra are assigned to transitions from the lowest 1(g) and 1(u) states to the X(1)0(+)(g) ground state. The X(2)1(g) --> X(1)0(+)(g) transition between the fine-structure components of the X(3)Sigma(-)(g) ground state must be magnetic dipole in nature and thus is the first purely magnetic dipole fine-structure transition observed in the optical region. The 1(u) state is mostly a component of the low-lying inverted A(3)Pi(u) state and so is denoted A(2)1(u). Vibrational analyses have yielded the following electronic energies and vibrational constants for (208)Pb(2) (in cm(-1)): X(1)0(+)(g): omega(e) = 110.20(2), omega(e)x(e) = 0.341(2); X(2)1(g): T(e) = 5304.9(1), omega(e) = 120.57(7), omega(e)x(e) = 0.254(14); A(2)1(u): T(e) = 7817.5(2), omega(e) = 126.45(6), omega(e)x(e) = 0.399(11), where the numbers in parentheses are the standard deviations of the parameters. Copyright 2000 Academic Press.     

Imaging of (13)C-labeled glucose and sorbitol in bovine lens by (1)H-detected (13)C nuclear magnetic resonance spectroscopy

Bovine lenses were incubated in a solution containing [1-(13)C]glucose (50 mM) for 1, 2 and 4 days. Spectroscopic images of [1-(13)C]glucose and [1-(13)C]sorbitol were constructed using (1)H-detected gradient-enhanced heteronuclear multiple-quantum coherence (GE-HMQC) in a 2.0-tesla magnetic field. Accumulations of [1-(13)C]glucose and [1-(13)C]sorbitol were mainly observed at the periphery of the lens. Their distributions corresponded to the cortex. (1)H-detected (13)C nuclear magnetic resonance (NMR) spectroscopic imaging by GE-HMQC successfully demonstrated the distribution of [1-(13)C]glucose and [1-(13)C]sorbitol at the periphery of bovine lenses.     

Practical choice of ¹H-¹H decoupling schemes in through-bond ¹H-{X} HMQC experiments at ultra-fast MAS

Three (1)H-(1)H homonuclear dipolar decoupling schemes for (1)H indirect detection measurements at very fast MAS are compared. The sequences require the following conditions: (i) being operable at very fast MAS, (ii) a long T(2)(') value, (iii) a large scaling factor, (iv) a small number of adjustable parameters, (v) an acquisition window, (vi) a low rf-power requirement, and (vii) a z-rotation feature. To satisfy these conditions a modified sequence named TIlted Magic-Echo Sandwich with zero degree sandwich pulse (TIMES(0)) is introduced. The basic elements of TIMES(0) consist of one sampling window and two phase-ramped irradiations, which realize alternating positive and negative 360° rotations of (1)H magnetization around an effective field tilted with an angle θ from the B(0) axis. The TIMES(0) sequence benefits from very large chemical shift scaling factors at ultra-fast MAS that reach κ(cs)=0.90 for θ=25° at ν(r)=80kHz MAS and only four adjustable parameters, resulting in easy setup. Long κ(cs)T(2)(') values, where T(2)(') is a irreversible proton transverse relaxation time, greatly enhance the sensitivity in (1)H-{(13)C} through-bond J-HMQC (Heteronuclear Multiple-Quantum Coherence) measurements with (1)H-(1)H decoupling during magnetization transfer periods. Although similar sensitivity can be obtained with through-space D-HMQC sequences, in which (13)C-(1)H dipolar interactions are recoupled, J-HMQC experiments incorporating (1)H-(1)H decoupling benefit from lower t(1)-noise, more uniform excitation of both CH, CH(2) and CH(3) moieties, and easier identification of through-bond connectivities.     

Non-uniformity correction of human brain imaging at high field by RF field mapping of B1+ and B1-

A new method of non-uniform image correction is proposed. Image non-uniformity is originated from the spatial distribution of RF transmission and reception fields, represented as B(1)(+) and B(1)(-), respectively. In our method, B(1)(+) mapping was performed invivo by a phase method. In B(1)(-) mapping, images with multiple TEs were acquired with a multi-echo adiabatic spin echo (MASE) sequence which enables homogeneous excitation. By T(2) fitting of these images an M(0) map (M(0)(MASE)) was obtained, in which signal intensity was expressed as the product of B(1)(-) and M?(1-e?(TR/T1)) . The ratio of this M(0)(MASE) map to the B(1)(+) map showed a similar spatial pattern in different human brains. These ratios of M(0)(MASE) to B(1)(+) in 24 subjects were averaged and then fitted with a spatially polynomial function to obtain a ratio map of B(1)(-)/B(1)(+)(α). Uniform image was achieved in spin echo (SE), MASE and inversion recovery turboFLASH (IRTF) images using measured B(1)(+) and calculated B(1)(-) by αB(1)(+). Water fractions in gray and white matters obtained from the M(0) images corrected by this method were in good agreement with previously reported values. From these experimental results, the proposed method of non-uniformity correction is validated at 4.7 T imaging.     

Evidence of Vibrational-Induced Rotational Axis Switching for HD(12)C(16)O: New High-Resolution Analysis of the nu(5) and nu(6) Bands and First Analysis of the nu(4) Band (10-µm Region)

Using new high-resolution Fourier transform spectra recorded in Giessen in the 8-12 μm region, a more extended analysis of the nu(5) and nu(6) bands and the first high-resolution study of the nu(4) band of HDCO were performed. As pointed out previously [M. Allegrini, J. W. C. Johns, and A. R. W. McKellar, Can. J. Phys. 56, 859-864 (1978)], the energy levels of the 5(1) and 6(1) states are strongly coupled by A- and B-type Coriolis interactions. On the other hand, it appeared that weaker resonances involving the energy levels of the 4(1) state with those of the 5(1) and 6(1) states also had to be accounted for. Consequently, the calculation of the energy levels was performed taking into account the Coriolis-type resonances linking the energy levels of the {6(1), 5(1), 4(1)} resonating states. Because of the unusually strong Coriolis interaction between nu(5) and nu(6), a nonclassical behavior of the rotational levels of the 5(1) and 6(1) states was observed and it was necessary to use a new Hamiltonian matrix which possesses, as usual, both A- and B-type Coriolis operators in the 5(1) if 6(1) and 6(1) if 4(1) off diagonal blocks but differs from the classical reduced Hamiltonian which is used commonly for planar C(s)-type molecules. More precisely, it proved necessary to include non-orthorhombic terms in the expansion of the rotational Hamiltonian of the 5(1) and 6(1) states. According to the considerations developed by Watson [J. K. G. Watson, in "Vibrational Spectra and Structure," (J. Durig, Ed.), Chap. 1, Elsevier, Amsterdam, 1977], these non-orthorhombic operators which are not symmetry forbidden are usually removed for semirigid C(s)-type molecules by rotational contact transformations. In the present study, the occurrence of terms in {J(x), J(z)} in the expansions of the rotational Hamiltonians for the 5(1) and 6(1) states indicates that the inertial system of HDCO differs for each of the three {6(1), 5(1), 4(1)} resonating states. Therefore, HDCO becomes a good example of vibrational-induced rotational axis switching (VIRAS) which was already suggested as the mechanism responsible for the enhanced densities of coupled states observed in 2-fluoroethanol [H. Li, S. Erza, and L. A. Philips, J. Chem. Phys. 97, 5956-5963 (1992)]. Copyright 2000 Academic Press.     

Evidence for strong-coupling s-wave superconductivity in MgB2: (11)B NMR Study

We have investigated a gap structure in a newly discovered superconductor, MgB2, through measurement of the (11)B nuclear spin-lattice relaxation rate, (11)(1/T(1)). (11)(1/T(1)) is proportional to the temperature (T) in the normal state, and decreases exponentially in the superconducting (SC) state, revealing a tiny coherence peak just below T(c). The T dependence of 1/T(1) in the SC state can be accounted for by an s-wave SC model with a large gap size of 2Delta/k(B)T(c) approximately 5 which suggests it is in a strong-coupling regime.     

Self-sum- and -difference-frequency mixing in GdAl(3)(BO(3))(4):Nd(3+) for generation of tunable ultraviolet and infrared radiation

We exploited Nd(3+) laser emission at 1061.9 nm ((4)F(3/2)?(4)I(11/2) channel) in a self-chi((2)) active GdAl(3)(BO(3))(4):Nd(3+) laser crystal. UV radiation was obtained from a 1.8% yield from self-sum-frequency mixing: 1/pump + 1/1061.9 = 1/UV, during pumping in the Nd(3+) (4)G(5/2)-(2)G(7/2) levels near 588 nm. The UV tunability had a range of 378-382 nm. We have demonstrated, for the first time to our knowledge, generation of coherent IR radiation from a self-difference-frequency mixing laser: 1/pump - 1/1061.9 = 1/IR. We got a 0.5% yield and tunability in the 1305-1365-nm range.     

Demonstration of a neonlike argon soft-x-ray laser with a picosecond-laser-irradiated gas puff target

We demonstrate a neonlike argon-ion x-ray laser, using a short-pulse laser-irradiated gas puff target. The gas puff target was formed by pulsed injection of gas from a high-pressure solenoid valve through a nozzle in the form of a narrow slit and irradiated with a combination of long, 600-ps and short, 6-ps high-power laser pulses with a total of 10 J of energy in a traveling-wave excitation scheme. Lasing was observed on the 3p (1)S(0)?3s (1)P(1) transition at 46.9 nm and the 3d (1)P(1)?3p (1)P(1) transition at 45.1 nm. A gain of 11 cm(-1) was measured on these transitions for targets up to 0.9 cm long.     

Thermal entanglement in the mixed three-spin XXZ Heisenberg model on a triangular cell

We numerically investigate the thermal entanglements of spins （1/2, 1） and spins （1/2, 1/2） in the three-mixed （1/2, 1, 1/2） anisotropic Heisenberg XXZ spin system on a simple triangular cell under an inhomogeneous magnetic field. We show that the external magnetic field induces strong plateau formation in the pairwise thermal entanglement for fixed parame-ters of the Hamiltonian in the cases of ferromagnetic and antiferromagnetic interactions. We also .observe an unexpected critical point at finite temperature in the thermal entanglement of spins （1/2, 1） for the antiferromagnetic case, while the entanglement of spins （1/2, 1） in the ferromagnetic case and the entanglement of spins （1/2, 1/2） in both ferromagnetic and antiferromagnetic cases almost decay exponentially to zero with increasing temperature. The critical point in the en-tanglement of spins （1/2, 1） in the antiferromagnetic case may be a signature of the quantum phase transition at finite temperature.