Gas Uptake and Thermodynamics in Porous Liquids Elucidated by 129Xe NMR.

We exploited 129Xe NMR to investigate xenon gas uptake and dynamics in a porous liquid formed by dissolving porous organic cages in a cavity-excluded solvent. Quantitative 129Xe NMR shows that when the amount of xenon added to the sample is lower than the amount of cages present (subsaturation), the porous liquid absorbs almost all xenon atoms from the gas phase, with 30% of the cages occupied with a Xe atom. A simple two-site exchange model enables an estimate of the chemical shift of 129Xe in the cages, which is in good agreement with the value provided by first-principles modeling. T2 relaxation times allow the determination of the exchange rate of Xe between the solvent and cage sites as well as the activation energies of the exchange. The 129Xe NMR analysis also enables determination of the free energy of confinement, and it shows that Xe binding is predominantly enthalpy-driven.

Melting of aqueous NaCl solutions in porous materials: shifted phase transition distribution (SIDI) approach for determining NMR cryoporometry pore size distributions.

Nuclear magnetic resonance cryoporometry (NMRC) and differential scanning calorimetry thermoporometry (DSC-TPM) are powerful methods for measuring mesopore size distributions. The methods are based on the fact that, according to the Gibbs-Thomson equation, the melting point depression of a liquid confined to a pore is inversely proportional to the pore size. However, aqueous salt solutions, which inherently exist in a broad range of biological porous materials as well as technological applications such as electrolytes, do not melt at a single temperature. This causes artefacts in the pore size distributions extracted by traditional Gibbs-Thomson analysis of NMRC and DSC-TPM data. Bulk aqueous NaCl solutions are known to have a broad distribution of melting points between the eutectic and pure water phase transition points (252-273 K). Here, we hypothesize that, when aqueous NaCl solution (saline) is confined to a small pore, the whole melting point distribution is shifted toward lower temperatures by the value predicted by the Gibbs-Thomson equation. We show that this so-called shifted phase transition distribution (SIDI) approach removes the artefacts arising from the traditional Gibbs-Thomson analysis and gives correct pore size distributions for saline saturated mesoporous silica gel and controlled pore materials analyzed by NMR cryoporometry. Furthermore, we demonstrate that the method can be used for determining pore sizes in collagen-chondroitin sulphate hydrogels resembling the composition of the extracellular matrix of articular cartilage. It is straightforward to apply the SIDI analysis for DSC-TMP data as well.

Unravelling the effect of paramagnetic Ni2+ on the 13C NMR shift tensor for carbonate in Mg2-xNixAl layered double hydroxides by quantum-chemical computations.

Structural disorder and low crystallinity render it challenging to characterise the atomic-level structure of layered double hydroxides (LDH). We report a novel multi-step, first-principles computational workflow for the analysis of paramagnetic solid-state NMR of complex inorganic systems such as LDH, which are commonly used as catalysts and energy storage materials. A series of 13CO32--labelled Mg2-xNixAl-LDH, x ranging from 0 (Mg2Al-LDH) to 2 (Ni2Al-LDH), features three distinct eigenvalues δ11, δ22 and δ33 of the experimental 13C chemical shift tensor. The δii correlate directly with the concentration of the paramagnetic Ni2+ and span a range of |δ11 - δ33| ≈ 90 ppm at x = 0, increasing to 950 ppm at x = 2. In contrast, the isotropic shift, δiso(13C), only varies by -14 ppm in the series. Detailed insight is obtained by computing (1) the orbital shielding by periodic density-functional theory involving interlayer water, (2) the long-range pseudocontact contribution of the randomly distributed Ni2+ ions in the cation layers (characterised by an ab initio susceptibility tensor) by a lattice sum, and (3) the close-range hyperfine terms using a full first-principles shielding machinery. A pseudohydrogen-terminated two-layer cluster model is used to compute (3), particularly the contact terms. Due to negative spin density contribution at the 13C site arising from the close-by Ni2+ sites, this step is necessary to reach a semiquantitative agreement with experiment. These findings influence future NMR investigations of the formally closed-shell interlayer species within LDH, such as the anions or water. Furthermore, the workflow is applicable to a variety of complex materials.

Scintillation Characteristics of the Single-Crystalline Film and Composite Film-Crystal Scintillators Based on the Ce3+-Doped (Lu,Gd)3(Ga,Al)5O12 Mixed Garnets under Alpha and Beta Particles, and Gamma Ray Excitations.

The crystals of (Lu,Gd)3(Ga,Al)5O12 multicomponent garnets with high density ρ and effective atomic number Zeff are characterized by high scintillation efficiency and a light yield value up to 50,000 ph/MeV. During recent years, single-crystalline films and composite film/crystal scintillators were developed on the basis of these multicomponent garnets. These film/crystal composites are potentially applicable for particle identification by pulse shape discrimination due to the fact that α-particles excite only the film response, γ-radiation excites only the substrate response, and ß-particles excite both to some extent. Here, we present new results regarding scintillating properties of selected (Lu,Gd)3(Ga,Al)5O12:Ce single-crystalline films under excitation by alpha and beta particles and gamma ray photons. We conclude that some of studied compositions are indeed suitable for testing in the proposed application, most notably Lu1.5Gd1.5Al3Ga2O12:Ce film on the GAGG:Ce substrate, exhibiting an α-particle-excited light yield of 1790-2720 ph/MeV and significantly different decay curves excited by α- and γ-radiation.

Hyper-CEST NMR of metal organic polyhedral cages reveals hidden diastereomers with diverse guest exchange kinetics.

Guest capture and release are important properties of self-assembling nanostructures. Over time, a significant fraction of guests might engage in short-lived states with different symmetry and stereoselectivity and transit frequently between multiple environments, thereby escaping common spectroscopy techniques. Here, we investigate the cavity of an iron-based metal organic polyhedron (Fe-MOP) using spin-hyperpolarized 129Xe Chemical Exchange Saturation Transfer (hyper-CEST) NMR. We report strong signals unknown from previous studies that persist under different perturbations. On-the-fly delivery of hyperpolarized gas yields CEST signatures that reflect different Xe exchange kinetics from multiple environments. Dilute pools with ~ 104-fold lower spin numbers than reported for directly detected hyperpolarized nuclei are readily detected due to efficient guest turnover. The system is further probed by instantaneous and medium timescale perturbations. Computational modeling indicates that these signals originate likely from Xe bound to three Fe-MOP diastereomers (T, C3, S4). The symmetry thus induces steric effects with aperture size changes that tunes selective spin manipulation as it is employed in CEST MRI agents and, potentially, impacts other processes occurring on the millisecond time scale.

The Czech version of the Utian Quality of Life Scale questionnaire assessing women's quality of life during menopause.

Introduction: Menopause is a physiological process, forming a part of a lifetime that most women go through. This period of life is briefly described by experts as a triple transformation: biological, social, and psychological. For menopausal women, health care professionals can use one of 10 specific questionnaires to assess health-related quality of life and its symptoms. The authors herein speak about the preparation of a Czech version of one such questionnaire - the Utian Quality of Life Scale (UQOL). Material and methods: A Czech version of the UQOL was created by repeated and backward translation. It was validated on a sample of 204 women after natural menopause (45-65 years old). We judged the reliability of the Czech version of UQOL using Cronbach's a. We assessed the instrument's validity by means of confirmation factor analysis. Results: The authors modified the original version of the UQOL. The Czech version has 4 new domains with 18 items. This form was created using the results of confirmation factor analysis. Conclusions: The Utian Quality of Life Scale questionnaire is completed by the women themselves, thus meeting the golden rule of all quality-of-life research stating that the primary source should be data from the client him/herself. However, this requirement raises some methodological problems.

Composite Detectors Based on Single-Crystalline Films and Single Crystals of Garnet Compounds.

This manuscript summarizes recent results on the development of composite luminescent materials based on the single-crystalline films and single crystals of simple and mixed garnet compounds obtained by the liquid-phase epitaxy growth method. Such composite materials can be applied as scintillating and thermoluminescent (TL) detectors for radiation monitoring of mixed ionization fluxes, as well as scintillation screens in the microimaging techniques. The film and crystal parts of composite detectors were fabricated from efficient scintillation/TL materials based on Ce3+-, Pr3+-, and Sc3+-doped Lu3Al5O12 garnets, as well as Ce3+-doped Gd3-xAxAl5-yGayO12 mixed garnets, where A = Lu or Tb; x = 0-1; y = 2-3 with significantly different scintillation decay or positions of the main peaks in their TL glow curves. This work also summarizes the results of optical study of films, crystals, and epitaxial structures of these garnet compounds using absorption, cathodoluminescence, and photoluminescence. The scintillation and TL properties of the developed materials under α- and ß-particles and γ-quanta excitations were studied as well. The most efficient variants of the composite scintillation and TL detectors for monitoring of composition of mixed beams of ionizing radiation were selected based on the results of this complex study.

Ab initio paramagnetic NMR shifts via point-dipole approximation in a large magnetic-anisotropy Co(ii) complex.

Transition metal complexes can possess a large magnetic susceptibility anisotropy, facilitating applications such as paramagnetic tags or shift agents in nuclear magnetic resonance (NMR) spectroscopy. Due to its g-shift and zero-field splitting (ZFS) we demonstrate on a Co(ii) clathrochelate with an aliphatic 16-carbon chain, a modern approach for ab initio calculation of paramagnetic susceptibility. Due to its large anisotropy, large linear dimension but relatively low number of atoms, the chosen complex is especially well-suited for testing the long-range point-dipole approximation (PDA) for the pseudocontact shifts (PCSs) of paramagnetic NMR. A static structure of the complex is used to compare the limiting long-distance PDA with full first-principles quantum-mechanical calculation. A non-symmetric formula for the magnetic susceptibility tensor is necessary to be consistent with the latter. Comparison with experimental shifts is performed by conformational averaging over the chain dynamics using Monte Carlo simulation. We observe satisfactory accuracy from the rudimentary simulation and, more importantly, demonstrate the fast applicability of the ab initio PDA.

Chemical shift extremum of 129Xe(aq) reveals details of hydrophobic solvation.

The 129Xe chemical shift in an aqueous solution exhibits a non-monotonic temperature dependence, featuring a maximum at 311 K. This is in contrast to most liquids, where the monotonic decrease of the shift follows that of liquid density. In particular, the shift maximum in water occurs at a higher temperature than that of the maximum density. We replicate this behaviour qualitatively via a molecular dynamics simulation and computing the 129Xe chemical shift for snapshots of the simulation trajectory. We also construct a semianalytical model, in which the Xe atom occupies a cavity constituted by a spherical water shell, consisting of an even distribution of solvent molecules. The temperature dependence of the shift is seen to result from a product of the decreasing local water density and an increasing term corresponding to the energetics of the Xe-H2O collisions. The latter moves the chemical shift maximum up in temperature, as compared to the density maximum. In water, the computed temperature of the shift maximum is found to be sensitive to both the details of the binary chemical shift function and the coordination number. This work suggests that, material parameters allowing, the maximum should be exhibited by other liquids, too.

Assignment of solid-state 13C and 1H NMR spectra of paramagnetic Ni(II) acetylacetonate complexes aided by first-principles computations.

Recent advances in computational methodology allowed for first-principles calculations of the nuclear shielding tensor for a series of paramagnetic nickel(II) acetylacetonate complexes, [Ni(acac)2L2] with L = H2O, D2O, NH3, ND3, and PMe2Ph have provided detailed insight into the origin of the paramagnetic contributions to the total shift tensor. This was employed for the assignment of the solid-state 1,2H and 13C MAS NMR spectra of these compounds. The two major contributions to the isotropic shifts are by orbital (diamagnetic-like) and contact mechanism. The orbital shielding, contact, as well as dipolar terms all contribute to the anisotropic component. The calculations suggest reassignment of the 13C methyl and carbonyl resonances in the acac ligand [Inorg. Chem.53, 2014, 399] leading to isotropic paramagnetic shifts of δ(13C) ≈ 800-1100 ppm and ≈180-300 ppm for 13C for the methyl and carbonyl carbons located three and two bonds away from the paramagnetic Ni(II) ion, respectively. Assignment using three different empirical correlations, i.e., paramagnetic shifts, shift anisotropy, and relaxation (T1) were ambiguous, however the latter two support the computational results. Thus, solid-state NMR spectroscopy in combination with modern quantum-chemical calculations of paramagnetic shifts constitutes a promising tool for structural investigations of metal complexes and materials.

Relativistic Approximations to Paramagnetic NMR Chemical Shift and Shielding Anisotropy in Transition Metal Systems.

We apply approximate relativistic methods to calculate the magnetic property tensors, i.e., the g-tensor, zero-field splitting (ZFS) tensor (D), and hyperfine coupling (HFC) tensors, for the purpose of constructing paramagnetic nuclear magnetic resonance (pNMR) shielding tensors. The chemical shift and shielding anisotropy are calculated by applying a modern implementation of the classic Kurland-McGarvey theory ( J. Magn. Reson. 1970 , 2 , 286 ), which formulates the shielding tensor in terms of the g- and HFC tensors obtained for the ground multiplet, in the case of higher than doublet multiplicity defined by the ZFS interaction. The g- and ZFS tensors are calculated by ab initio complete active space self-consistent field and N-electron valence-state perturbation theory methods with spin-orbit (SO) effects treated via quasidegenerate perturbation theory. Results obtained with the scalar relativistic (SR) Douglas-Kroll-Hess Hamiltonian used for the g- and ZFS tensor calculations are compared with nonrelativistically based computations. The HFC tensors computed using the fully relativistic four-component matrix Dirac-Kohn-Sham approach are contrasted against perturbationally SO-corrected nonrelativistic results in the density functional theory framework. These approximations are applied on paramagnetic metallocenes (MCp2) (M = Ni, Cr, V, Mn, Co, Rh, Ir), a Co(II) pyrazolylborate complex, and a Cr(III) complex. SR effects are found to be small for g and D in these systems. The HFCs are found to be more influenced by relativistic effects for the 3d systems. However, for some of the 3d complexes, nonrelativistic calculations give a reasonable agreement with the experimental chemical shift and shielding anisotropy. The influence of scalar relativity is strong for the 5d IrCp2 system. This mixed ab initio/DFT technique, with a fully relativistic method used for the critical HFC tensor, should be useful for the treatment of both electron correlation and relativistic effects at a reasonable computational cost to compute the pNMR shielding tensors in transition metal systems.

Pseudo-Contact NMR Shifts over the Paramagnetic Metalloprotein CoMMP-12 from First Principles.

Long-range pseudo-contact NMR shifts (PCSs) provide important restraints for the structure refinement of proteins when a paramagnetic metal center is present, either naturally or introduced artificially. Here we show that ab initio quantum-chemical methods and a modern version of the Kurland-McGarvey approach for paramagnetic NMR (pNMR) shifts in the presence of zero-field splitting (ZFS) together provide accurate predictions of all PCSs in a metalloprotein (high-spin cobalt-substituted MMP-12 as a test case). Computations of 314 13 C PCSs using g- and ZFS tensors based on multi-reference methods provide a reliable bridge between EPR-parameter- and susceptibility-based pNMR formalisms. Due to the high sensitivity of PCSs to even small structural differences, local structures based either on X-ray diffraction or on various DFT optimizations could be evaluated critically by comparing computed and experimental PCSs. Many DFT functionals provide insufficiently accurate structures. We also found the available 1RMZ PDB X-ray structure to exhibit deficiencies related to binding of a hydroxamate inhibitor. This has led to a newly refined PDB structure for MMP-12 (5LAB) that provides a more accurate coordination arrangement and PCSs.

Czech version of OPQOL-35 questionnaire: the evaluation of the psychometric properties.

BACKGROUND: Both prognoses and real demographic trends in developed countries point to the increasing proportion in the population of people above 65 years of age. One of important themes of care for seniors is the assessment of their quality of life. To evaluate the quality of life of seniors three types of tools can be used: general generic tools; generic tools used for the age group of elderly persons; specific tools to detect the quality of life of the elderly who are affected by specific diseases. METHODS: The second type of tool is represented by the OPQOL - 35 questionnaire (Older People's Quality of Life Questionnaire), which was developed in the UK. It has 35 items and deals with 8 domains of quality of life. With the consent of the author the questionnaire was translated into Czech and verified in a group of 478 seniors aged 60 and above (40 % males, 60 % females). Unlike the British version, the Czech version has seven factors: 1 Role of belief, religion and culture; 2 Health; independence, active life; 3 Financial situation; 4 Family and safe environment; 5 Loneliness; 6 Satisfaction with life; 7 Positive approach to life. RESULTS: The Czech version has a very good reliability (Cronbach's alpha ranges from .726 to .905). It also has satisfactory validity. The results show that with increasing age and number of health problems the satisfaction of the elderly is declining in all seven domains. Conversely, the degree of autonomy in the way of living is positively associated with the satisfaction of seniors. Old people who live alone at home, are self-sufficient and do not need the help of others, are more satisfied with their quality of life than other seniors (i.e..those who are living with their children, in sheltered accommodation or in homes for the elderly). Single, married seniors and seniors with a partner are happier than the widowed ones. CONCLUSIONS: The questionnaire gives good guidance for assessing the current state of the quality of life of seniors, changes in quality over time and for targeted interventions as well.

Magnetic couplings in the chemical shift of paramagnetic NMR.

We apply the Kurland-McGarvey (J. Magn. Reson. 1970, 2, 286) theory for the NMR shielding of paramagnetic molecules, particularly its special case limited to the ground-state multiplet characterized by zero-field splitting (ZFS) interaction of the form S·D·S. The correct formulation for this problem was recently presented by Soncini and Van den Heuvel (J. Chem. Phys. 2013, 138, 054113). With the effective electron spin quantum number S, the theory involves 2S+1 states, of which all but one are low-lying excited states, between which magnetic couplings take place by Zeeman and hyperfine interactions. We investigate these couplings as a function of temperature, focusing on both the high- and low-temperature behaviors. As has been seen in work by others, the full treatment of magnetic couplings is crucial for a realistic description of the temperature behavior of NMR shielding up to normal measurement temperatures. At high temperatures, depending on the magnitude of ZFS, the effect of magnetic couplings diminishes, and the Zeeman and hyperfine interactions become effectively averaged in the thermally occupied states of the multiplet. At still higher temperatures, the ZFS may be omitted altogether, and the shielding properties may be evaluated using a doublet-like formula, with all the 2S+1 states becoming effectively degenerate at the limit of vanishing magnetic field. We demonstrate these features using first-principles calculations of Ni(II), Co(II), Cr(II), and Cr(III) complexes, which have ZFS of different sizes and signs. A non-monotonic inverse temperature dependence of the hyperfine shift is predicted for axially symmetric integer-spin systems with a positive D parameter of ZFS. This is due to the magnetic coupling terms that are proportional to kT at low temperatures, canceling the Curie-type 1/kT prefactor of the hyperfine shielding in this case.

¹H Chemical Shifts in Paramagnetic Co(II) Pyrazolylborate Complexes: A First-Principles Study.

We apply the theory of the nuclear magnetic resonance (NMR) chemical shift for paramagnetic systems to demanding cobalt(II) complexes. Paramagnetic NMR (pNMR) chemical shift results by density-functional theory (DFT) can be very far from the experimental values. Therefore, it is of interest to investigate the applicability of electron-correlated ab initio computational methods to achieve useful accuracy. Here, we use ab initio wave function based electronic structure methods to calculate the pNMR chemical shift within the theoretical framework established recently. We applied the N-electron valence-state perturbation theory (NEVPT2) on three Co(II) systems, where the active space of the underlying complete active space self-consistent field (CASSCF) wave function consists of seven electrons in the five metal 3d orbitals. These complexes have the S = 3/2 electronic ground state consisting of two doublets separated by zero-field splitting (ZFS). To calculate the hyperfine coupling tensor A, DFT was used, while the g- and ZFS-tensors were calculated using the ab initio CASSCF and NEVPT2 methods. These results were combined to obtain the total chemical shifts. The shifts obtained from these calculations are in generally good agreement with the experimental results, in some cases suggesting a reassignment of the signals. The accuracy of this mixed ab initio/DFT approach is very promising for further applications to demanding pNMR problems involving transition metals.

Spin Doublet Point Defects in Graphenes: Predictions for ESR and NMR Spectral Parameters.

An adatom on a graphene surface may carry a magnetic moment causing spin-half paramagnetism. This theoretically predicted phenomenon has recently also been experimentally verified. The measurements of defect-induced magnetism are mainly based on magnetometric techniques where artifacts such as environmental magnetic impurities are hard to rule out. Spectroscopic methods such as electron spin resonance (ESR) and paramagnetic nuclear magnetic resonance (pNMR) are conventionally used in the development of magnetic materials, e.g., to study paramagnetic centers. The present density functional theory study demonstrates with calculations of the ESR g-tensor and the hyperfine coupling tensors, as well as the pNMR shielding tensor, that these spectroscopies can be used to identify the paramagnetic centers in graphenes. The studied defects are hydrogen and fluorine adatoms on sp(2)-hybridized graphene, as well as hydrogen and fluorine vacancies in the sp(3)-hybridized graphane and fluorographene, respectively. The directly measurable ESR and pNMR parameters give insight into the electronic and atomic structures of these defects and may contribute to understanding carbon-based magnetism via the characterization of the defect centers. We show that missing hydrogen and fluorine atoms in the functionalized graphane and fluorographene, respectively, constitute sp(2)-defect centers, in which the magnetic resonance parameters are greatly enhanced. Slowly decaying adatom-induced magnetic resonance parameters with the distance from the sp(3)-defect, are found in pure graphene.

Treated Autoimmune Thyroid Disease Is Associated with a Decreased Quality of Life among Young Persons with Type 1 Diabetes.

Type 1 diabetes (T1D) in children and adolescents is relatively often accompanied by other immunopathological diseases, autoimmune thyroid disease (AITD) or celiac disease (CD). Our aim was to assess whether these conditions are associated with changes in the health-related quality of life (HRQOL) in pediatric patients with T1D. In a cross-sectional study we identified eligible 332 patients with T1D aged 8-18 years, of whom 248 (75%) together with their parents responded to the PedsQL Generic and Diabetes Modules. Compared to 143 patients without thyroid autoantibodies, 40 patients with a thyroxine-treated AITD scored lower in the overall generic HRQOL (P = 0.014), as well as in the overall diabetes-specific HRQOL (P = 0.013). After adjustment for age, gender, duration of diabetes, type of diabetes treatment, and diabetes control, this association remained statistically significant for the generic HRQOL (P = 0.023). Celiac disease was not associated with a change in the generic or diabetes-specific HRQOL (P = 0.07 and P = 0.63, resp.). Parental scores showed no association with AITD or celiac disease, except a marginally significant decrease in the overall generic HRQOL (P = 0.039) in the T1D + AITD compared to T1D group. Our study indicates that, in pediatric patients with T1D, concomitant thyroxine-treated AITD is associated with lower quality of life.

[Positive aspects of old ages - humor of seniors]. / Pozitivní aspekty stárí: seniori a humor.

This survey study has five parts. In the first part two conceptual approaches to humor are characterized. One considers "the comic" to be an umbrella concept, and humor is only one of its rather positive forms. The other comes out from the umbrella concept "humor", and distinguishes between various forms of humor including the negative ones. Three main theories of humor are presented: theory of superiority, theory of incongruity, and a relief theory. The second part introduces humor in the elderly and draws the attention to the fact that we know relatively little about humor in old age because most research has been carried out in children, adolescents or adults in productive age. The third part of the study describes the process of diagnostics of humor in the elderly. For example, within the qualitative methods, in-depth interviews with seniors or analyses of their diary entries are used. Within quantitative methods, questionnaires are used, and this study presents the survey of seven most frequent ones applied in the studies of humor in the elderly. In the context of mixed methods, understanding of humor in young and seniors, or understanding of humor in relatively healthy seniors and seniors after stroke are compared. The fourth part of the study presents the Gelkopfs model on relationship between humor, treatment and cure of patients. The fifth part of the study demonstrates the options how to use humor to improve the mental state of the elderly (by means of individual or group interventions).

Solvation chemical shifts of perylenic antenna molecules from molecular dynamics simulations.

Solvation-induced shifts in molecular properties can be realistically simulated by employing a dynamic model with explicit solvent molecules. In this work, (13)C NMR chemical shifts of various candidate antenna molecules for dye-sensitised solar cells have been studied by using density-functional theory calculations both in vacuo and by employing a dynamic solvation model. The solvent effects were investigated using instantaneous molecular dynamics snapshots containing the antenna molecule and surrounding acetonitrile solvent molecules. Such calculations take into account the main mechanisms of solvation-induced chemical shifts. We have analysed the contributions to the solvent shift due to the solvent susceptibility anisotropy, changes in the density of the virtual orbital space and the accessibility of the excited states to the pronouncedly local magnetic hyperfine operator. We present Lorentzian-broadened chemical shift stick spectra in which a comparison of the in vacuo and dynamic-solvation model results is graphically illustrated. The results show that the solvent-accessible atoms at the perimeter of the solute are influenced by the virtual states of the solvent molecules, which are visible to the hyperfine operators of the perimeter nuclei. This enables efficient coupling of the ground state of the solute to the magnetically allowed excited states, resulting in a positive chemical shift contribution of the perimeter nuclei. As a result of solvation, the chemical shift signals of perimeter nuclei are found to be displaced towards larger chemical shift values, whereas the nuclei of the inner region of the solute molecules show the opposite trend. The solvent susceptibility anisotropy is found to cause a small and practically constant contribution.

Spin dynamics simulation of electron spin relaxation in Ni²âº(aq).

The ability to quantitatively predict and analyze the rate of electron spin relaxation of open-shell systems is important for electron paramagnetic resonance and paramagnetic nuclear magnetic resonance spectroscopies. We present a combined molecular dynamics (MD), quantum chemistry (QC), and spin dynamics simulation method for calculating such spin relaxation rates. The method is based on the sampling of a MD trajectory by QC calculations, to produce instantaneous parameters of the spin Hamiltonian used, in turn, to numerically solve the Liouville-von Neumann equation for the time evolution of the spin density matrix. We demonstrate the approach by simulating the relaxation of electron spin in an aqueous solution of Ni(2+) ion. The spin-lattice (T1) and spin-spin (T2) relaxation rates are extracted directly from the simulations of the time dependence of the longitudinal and transverse magnetization, respectively. Good agreement with the available, indirectly obtained experimental data is obtained by our method.