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1.
Hanni M Lantto P Runeberg N Jokisaari J Vaara J 《The Journal of chemical physics》2004,121(12):5908-5919
Quantum chemical calculations of the nuclear shielding tensor, the nuclear quadrupole coupling tensor, and the spin-rotation tensor are reported for the Xe dimer using ab initio quantum chemical methods. The binary chemical shift delta, the anisotropy of the shielding tensor Delta sigma, the nuclear quadrupole coupling tensor component along the internuclear axis chi( parallel ), and the spin-rotation constant C( perpendicular ) are presented as a function of internuclear distance. The basis set superposition error is approximately corrected for by using the counterpoise correction (CP) method. Electron correlation effects are systematically studied via the Hartree-Fock, complete active space self-consistent field, second-order M?ller-Plesset many-body perturbation, and coupled-cluster singles and doubles (CCSD) theories, the last one without and with noniterative triples, at the nonrelativistic all-electron level. We also report a high-quality theoretical interatomic potential for the Xe dimer, gained using the relativistic effective potential/core polarization potential scheme. These calculations used valence basis set of cc-pVQZ quality supplemented with a set of midbond functions. The second virial coefficient of Xe nuclear shielding, which is probably the experimentally best-characterized intermolecular interaction effect in nuclear magnetic resonance spectroscopy, is computed as a function of temperature, and compared to experiment and earlier theoretical results. The best results for the second virial coefficient, obtained using the CCSD(CP) binary chemical shift curve and either our best theoretical potential or the empirical potentials from the literature, are in good agreement with experiment. Zero-point vibrational corrections of delta, Delta sigma, chi (parallel), and C (perpendicular) in the nu=0, J=0 rovibrational ground state of the xenon dimer are also reported. 相似文献
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Mikael Mohtaschemi Anni Sorvari Antti Puisto Markus Nuopponen Jukka Seppälä Mikko J. Alava 《Cellulose (London, England)》2014,21(6):3913-3925
We conduct rheological characterization of nanofibrillated cellulose (NFC) suspensions, a highly non-Newtonian complex fluid, at several concentrations. Special care is taken to cope with the prevalent problems of time scale issues, wall depletion and confinement effects. We do this by combining the wide-gap vane geometry, extremely long measurement times, and modeling. We take into account the wide-gap related stress heterogeneity by extending upon mainstream methods and apply a gap correction. Furthermore, we rationalize the experimental data through a simple viscous structural model. With these tools we find that, owing to the small size of the particles subjected to Brownian motion, the NFC suspensions exhibit a critical shear rate, where the flow curve experiences a turning point. This makes the steady state of these suspensions at low shear rates non-unique. To optimize various mixing and pumping applications, such history dependent tendency of NFC suspensions to shear band needs to be taken into account. 相似文献
4.
Jukka J. Remes Ahmed Abou Elseoud Esa Ollila Marianne Haapea Tuomo Starck Juha Nikkinen Osmo Tervonen Olli Silven 《Magnetic resonance imaging》2013,31(8):1338-1348
Subject-level resting-state fMRI (RS-fMRI) spatial independent component analysis (sICA) may provide new ways to analyze the data when performed in the sliding time window. However, whether principal component analysis (PCA) and voxel-wise variance normalization (VN) are applicable pre-processing procedures in the sliding-window context, as they are for regular sICA, has not been addressed so far. Also model order selection requires further studies concerning sliding-window sICA. In this paper we have addressed these concerns. First, we compared PCA-retained subspaces concerning overlapping parts of consecutive temporal windows to answer whether in-window PCA and VN can confound comparisons between sICA analyses in consecutive windows. Second, we compared the PCA subspaces between windowed and full data to assess expected comparability between windowed and full-data sICA results. Third, temporal evolution of dimensionality estimates in RS-fMRI data sets was monitored to identify potential challenges in model order selection in a sliding-window sICA context. Our results illustrate that in-window VN can be safely used, in-window PCA is applicable with most window widths and that comparisons between windowed and full data should not be performed from a subspace similarity point of view. In addition, our studies on dimensionality estimates demonstrated that there are sustained, periodic and very case-specific changes in signal-to-noise ratio within RS-fMRI data sets. Consequently, dimensionality estimation is needed for well-founded model order determination in the sliding-window case. The observed periodic changes correspond to a frequency band of ≤ 0.1 Hz, which is commonly associated with brain activity in RS-fMRI and become on average most pronounced at window widths of 80 and 60 time points (144 and 108 s, respectively). Wider windows provided only slightly better comparability between consecutive windows, and 60 time point or shorter windows also provided the best comparability with full-data results. Further studies are needed to determine the cause for dimensionality variations. 相似文献
5.
Nikolaos Pahimanolis Arto Salminen Paavo A. Penttilä Juuso T. Korhonen Leena-Sisko Johansson Janne Ruokolainen Ritva Serimaa Jukka Seppälä 《Cellulose (London, England)》2013,20(3):1459-1468
In this paper, nanofibrillated cellulose/carboxymethyl cellulose (CMC) composite films were prepared using tape casting. The obtained transparent films showed shear induced partial alignment of fibrils along the casting direction, resulting in birefringence in cross polarized light. The carboxyl groups of CMC could be further utilized to create ionic crosslinking by treatment with glycidyl trimethyl ammonium chloride (GTMA). The GTMA treated composite films had improved mechanical properties both in wet and dry state. The chemical composition and morphologies of composites were analyzed with X-ray photoelectron spectroscopy, elemental analysis, scanning electron microscopy and wide-angle X-ray scattering. 相似文献
6.
Saunavaara J Jokisaari J 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2006,180(1):58-62
The (129)Xe chemical shift of xenon dissolved in isotropic liquids is very sensitive to solvent density, which in turn is dependent on the sample temperature. Therefore, the (129)Xe chemical shift can be used as the basis of a thermometer for measuring actual sample temperatures in NMR experiments. Good accuracy can be achieved, but the thermometer is particularly useful in monitoring temperature stability. In the present case, carbon tetrachloride (CCl(4)), ethylbromide (C(2)H(5)Br), and deuterated chloroform (CDCl(3)) were chosen as solvents because of their large thermal expansion coefficient. 相似文献
7.
We study the effects of a gate-controlled Rashba spin-orbit coupling to quantum spin Hall edge states in HgTe quantum wells. A uniform Rashba coupling can be employed in tuning the spin orientation of the edge states while preserving the time-reversal symmetry. We introduce a sample geometry where the Rashba coupling can be used in probing helicity by purely electrical means without requiring spin detection, application of magnetic materials or magnetic fields. In the considered setup a tilt of the spin orientation with respect to the normal of the sample leads to a reduction in the two-terminal conductance with current-voltage characteristics and temperature dependence typical of Luttinger liquid constrictions. 相似文献
8.
We study optimal stopping with exponentially distributed exercise lag. We formalize the problem first in a general Markovian
setting and derive a set of conditions under which the solution exists. In particular, no semicontinuity assumptions of the
payoff function are needed. We analyze also some specific classes of lagged optimal stopping problems with one-dimensional
diffusion dynamics where the solution can be characterized in closed form. Finally, the results are illustrated with an explicit
example. 相似文献
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