H NMR relaxation in urea

Proton NMR spin–lattice relaxation times T₁ were measured for urea as a function of temperature. An activation energy of 46.3 ± 4.7 kJ/mol was extracted and compared with the range of 38–65 kJ/mol previously reported in the literature as measured by different magnetic resonance techniques. In addition, proton NMR spin–lattice relaxation times in the rotating frame T_1ρ were measured as a function of temperature. These measurements provide acquisition conditions for the ¹³C and ¹⁵N CP/MAS spectra of pure urea in the crystalline phase.     

H and H NMR studies of cyclohexane nanocrystals in controlled pore glasses

The formation and behaviour of cyclohexane and cyclohexane-d₁₂ nanocrystals in mesoporous solids of well-defined dimensional constraints are studied by ¹H and ²H NMR. The NMR line widths, spin–spin relaxation times (T₂), spin–lattice relaxation times (T₁) and diffusivities (D) were measured as a function of temperature, and the results are discussed with reference to the values obtained for the bulk materials. The confined solids exhibit substantial changes in the phase behaviour and molecular dynamics. Thus, the line-shape measurements reveal a two-phase system consisting of a highly mobile component at the surface of the pore and a plastically crystalline phase in the centre of the pore. The liquid-like surface layer in the mesopores is observable well below the reduced transition temperature of the confined cyclohexane. However, the T₂ and diffusion measurements show that the mobile phase also embraces a minor component attributed to non-frozen liquid in pockets or offshoots.     

Effects of inorganic components on the structure and thermo-oxidative degradation of PMMA modified metal alkoxide–EAA complex

Poly(methyl methacrylate) (PMMA) modified titanium and zirconium n-butoxide–ethyl acetoacetate (EAA) complex [M5-Ti(OBuⁿ)₂(EAA)₂ and M5-Zr(OBuⁿ)₂(EAA)₂] were obtained from trialkoxysilane-functional PMMA and EAA modified titanium and zirconium alkoxide via the sol–gel method. Infrared (IR), ¹³C nuclear magnetic resonance (NMR) spectroscopy, and thermogravimetric analysis (TGA) were used to analyze the structures and properties of the hybrids with various proportions of metal oxide species. The effect of the complex of metal oxides and EAA ligands on structure and thermo-oxidative degradation of the M5-Ti(OBuⁿ)₂(EAA)₂ and M5-Zr(OBuⁿ)₂(EAA)₂ hybrids were investigated in this study. The ¹H spin–diffusion path length of the hybrids was in a nanometer scale as estimated from the spin–lattice relaxation time in a rotating frame (T_1ρ^H). The apparent activation energies (E_a), evaluated by van Krevelen’s method, for random scission of PMMA segments in hybrids decreased with increasing metal oxide content.     

Molecular motion and phase transition in perovskite-type (CH3)nNH4−nSnCl3 (n=1–4) studied by proton NMR spin–lattice relaxation

Powder X-ray diffraction, ¹¹⁹Sn NMR spectra, and ¹H NMR spin–lattice relaxation times, T₁, were measured for (CH₃)_nNH_4−nSnCl₃ (n=1–4). From the Rietveld analysis, it is shown that all four compounds crystallize into deformed perovskite-type structures at room temperature. The temperature dependence of ¹H T₁ was analyzed in terms of the CH₃ reorientation and other motions of the whole cation. Except for the phase transition in CH₃NH₃SnCl₃, which is from monoclinic to rhombohedral at 331 K, ¹H T₁ was continuously changed at other phase transitions in this compound as well as in the n=2–4 compounds, suggesting that the transitions are not caused by the change of the motional state of the cation but by an instability of the [SnCl₃]_nⁿ⁻ perovskite lattice.     

H NMR study of hydrogen bonding and molecular dynamics of 5CB confined to molecular sieves

It has been found that the main mechanism of ¹H protons spin–lattice relaxation of bulk 5CB at 200 MHz is its intramolecular motion, namely, the reorientation of CH₂ and CH₃ groups of its alkyl chain. Activation parameters of such motions have been estimated.

Drastic decrease in proton spin–lattice relaxation times at the nematic-to-isotropic phase transition can be explained by the activation of molecular translational diffusion and reorientations around long and short molecular axes of bulk 5CB.

Our NMR analysis revealed the slowing-down of molecular dynamics of confined 5CB molecules and their fragments. This can be explained by the interaction of some part of 5CB molecules with the surface active Si(Al)–OH centers of MCM matrix via hydrogen bonds of Si(Al)–OHN≡C-type.     

Microdynamics of solid anilinium chloride

Intraionic C₃ reorientation of the anilinium NH⁺₃ group was evidenced by measurements of the temperature dependence of the proton spin—lattice relaxation time, by rotating frame experiments and cw NMR data. Analysis of the results yielded a rotor hindering potential E = 33.6 kJ/mole and τ_o = 4 × 10⁻¹³ s.     

The anisotropy of the spin—lattice relaxation in the lowest triplet state of naphthalene in durene in the presence of a magnetic field

We have measured the spin—lattice relaxation rates in the phosphorescent triplet state T_o of naphthalene in durene as a function of the direction of the magnetic field. The orientational dependence of the relaxation is explained by thermal activation to a close lying local phonon state where the spin axes are rotated with respect to those in T_o.     

Investigation of the proton mobility in CsH(SO4)0.76(SeO4)0.24 crystal by H NMR spectroscopy

Crystals of CsH(SO₄)_0.76(SeO₄)_0.24 formulation were studied by ¹H NMR spectroscopy. The ¹H line-shape, the T₁ and T₂ relaxation times were determined as a function of temperature. The activation energies deduced from the temperature dependence of relaxation times were compared with the activation energy issued from conductivity measurements. The results obtained are discussed and supported by the Ngai model.     

Photodissociation spectroscopy of Mg—Ar

Mg⁺—Ar ion—molecule complexes are produced in a pulsed supersonic nozzle cluster source. The complexes are mass selected and studied with laser photodissociation spectroscopy in a reflectron time-of-flight mass spectrometer system. An electronic transition assigned as X ²Σ⁺ → ²Π is observed with an origin at 31387 cm⁻¹ (vac) for ²⁴Mg⁺—Ar. The ²⁴Mg⁺—Ar spectrum is characterized by a 15 member progression with a frequency (ω′_e) of 272 cm⁻¹. An extrapolation of this progression fixes the excited state dissociation energy (D′_o) at 5552 cm⁻¹. The corresponding ground-state value (D″_o) is 1270 cm⁻¹ (3.6 kcal/mol). The ²Π _, spin—orbit splitting is 76 cm⁻.     

Singlet—triplet radiationless processes in glyoxal in the presence of a magnetic field

The magnetic quenching of fluorescence in glyoxal is studied under the single-rotational level excitation. It is shown that the magnetic effect saturates in the fields inducing a complete spin—rotation decoupling evidenced in a study of the Zeeman effect in the ³A_u ← ¹A_u transition. The increase of the collision-induced intersystem crossing rate k_ISC may be accounted for by a magnetic mixing of triplet sublevels (only partially mixed by rotation) in the specific case, of a non-linear dependence of k_ISC on the singlet—triplet mixing coefficients.     

State and velocity distributions of Cl atoms produced in the photodissociation of ICI at 237 nm

Photofragment spectroscopy of ICI molecules photodissociated at 237 nm is studied by 2 + 1 resonance-enhanced multi-photon ionization and time of flight techniques. Doppler profiles of the chlorine atom fragments in two spin—orbit states show that chlorine atoms in the ground state, ²P_3/2, are produced from a perpendicular dissociative transition, and chlorine atoms in the excited state, ²P , arise from a parallel transition. The possible electronically excited states leading to dissociation in both the perpendicular and parallel cases are considered.     

用13C的NMR T1研究苯环上甲基的内旋转

提出了通过对样品进行邻位取代和间位取代以从实验上测定自旋-内旋转弛豫速率的处理方法.在28-90℃的温度范围内测量了邻二甲苯和间二甲苯的甲基碳的T₁和NOE因子.分离得间二甲苯上甲基碳的自旋-内旋转弛豫速率和自旋-整体旋转弛豫速率,并计算得甲基的内旋转速率.     

Molecules in high spin states II: the pure rotational spectrum of MnF (XΣ)

The pure rotational spectrum of MnF has been measured in its X⁷Σ⁺ ground state using millimeter/sub-millimeter direct absorption methods. Five and six rotational transitions, respectively, were recorded for this radical in its v=0 and v=1 states in the range 338–630 GHz. MnF was created from SF₆ and manganese vapor, produced in a Broida-type oven. The species exhibited a complex pattern where the fine and ⁵⁵Mn and ¹⁹F hyperfine structures are intermixed. Rotational, spin–rotation, spin–spin and hyperfine parameters have been determined for MnF. These constants have been interpreted in terms of bonding and electronic structure in metal fluorides.     

Zero-field splitting in molecules with closely spaced triplet states : A theoretical investigation of three isomeric dimethylbenzaldehydes

It is shown by quantum-chemical calculations that the unusually large zero-field splitting observed in ³ππ^* states of 2,4-, 2,5- and 3,4-dimethylbenzaldehyde are mainly due to second-order spin—orbit coupling with ³nπ^* states modulated by Franck—Condon factors.     

Dynamics of 4,4'-di-n-heptylazoxybenzene (HAB) studied using dielectric and 2H NMR relaxation measurements

Results of studies of 4,4'-di-n-heptylazoxybenzene (HAB) in the isotropic, nematic and smectic A phases are presented. Two experimental methods were employed: broad band dielectric spectroscopy and nuclear magnetic resonance spectroscopy. The complex dielectric permittivity, ε*(ω)=ε'(ω)-iε'(ω), was measured in the frequency range 1 kHz-4 GHz. This allowed two main relaxation processes to be separated in all the phases studied: the low frequency (l. f.) process connected with molecular reorientations around the short axes, and the high frequency (h. f.) process connected with the rotations around the long axes. The corresponding relaxation times and activation enthalpies were obtained. The l. f. relaxation time changes step-wise at the phase transitions, whereas the h. f. relaxation time passes smoothly through all the phases. The measurement of ²H spin-lattice relaxation times was carried out throughout the mesophase range at 61.38 MHz. These data were analysed together with the relaxation times measured at 10.00 and 46.04 MHz, available from previous studies. Using suitable theoretical models the principal components of the diffusional tensor, D_‖ and D_⊥, as well as the diffusion coefficients D_R relative to the internal rotation of the phenyl rings, were determined. The results of both studies are compared and discussed.     

C and H nuclear magnetic shielding and spin–spin coupling constants of C-enriched bromomethane in the gas phase

¹³C and ¹H NMR spectral parameters are investigated for ¹³CH₃Br in gaseous matrices. It is found that both the ¹³C and ¹H chemical shifts of ¹³CH₃Br are linearly dependent on solvent density. Similar dependence is also detected for one-bond spin–spin coupling, ¹J(CH). For the first time the ¹³C and ¹H magnetic shielding constants and ¹J(CH) spin–spin coupling are obtained for an isolated ¹³CH₃Br molecule together with the coefficients responsible for solute–solvent molecular interactions in gaseous matrices. The present experimental results confirm the accuracy of some recent ab initio calculations of nuclear magnetic shielding performed for bromomethane.     

Field-cycling NMR detection of magnetoacoustically manipulated nematic ordered states: Memory effects

The proton spin–lattice relaxation time (T₁) dispersion was studied under simultaneous sonication in the nematic phase of 5CB. It appears that metastable ordered states subject to a memory effect can be induced by the combined action of an amplitude-modulated ultrasonication and a pulsed magnetic field. We argue that the acoustic amplitude modulation adds instability to the nematic phase through director order fluctuation enhancement. Different manipulated states of the director were unambiguously identified by the Larmor frequency dispersion of T₁. The field-cycling NMR technique was used for T₁ measurements.     

Spectroscopic study of harmane in micelles at 77 K using fluorescent probes

Steady-state and time-resolved emission for spectroscopic techniques at 77 K, and molecular orbital calculations using PM3-MOPAC/93 and HAM/3-CI have been used to study the two forms of harmane, the neutral (HN) and the monoprotonated (HH), in different environments. In hydrophobic media, for (HN), four species were determined and in hydrophilic medium, for (HH), we found just one species. The photophysical properties of all these species were determined, and we verified that each one of them displays distinct photophysical properties from one to another. For example, for monomer of (HN), the lowest electronic singlet state S₁ is (π,π^*) and the lowest electronic triplet state T₁ is (π,π^*), due to the phosphorescence lifetime it is t=0.8 s. For the (HH) monomer, the S₁ is (π,π^*) and T₁ is (π,π^*) and the spin–orbital coupling is inefficient. These determinations were used to characterise and to identify the harmane species that is solubilised into the interior of neutral (triton X-100), anionic (dodecyl lithium sulphate) and cationic (hexadecyltrimethyl ammonium bromide) micelles, all of them were prepared under physiological conditions. The results indicated that active species in the interior of the micelles is a hydrogen bond complex between (HN) and micellar environments that is anchored in the aqueous region of micelles.     

Molecular determinants for drug-receptor interactions. 8. Anisotropic and internal motions in morphine, nalorphine, oxymorphone, naloxone and naltrexone in aqueous solution by carbon-13 NMR spin-lattice relaxation times

Carbon-13 NMR spin-lattice relaxation times (T₁) were measured for morphine, oxymorphone, nalorphine, naloxone and naltrexone as hydrochloride salts in ²H₂O solution. The data refer to the molecules in the N-equatorial configuration. The experimental T₁ values were interpreted using a model of anisotropic reorientation of a rigid body with superimposed internal motions of the flexible N-methyl, N-methyl-allyl and N-methyl-cyclopropyl fragments. The calculated internal motional rates were found to markedly decrease on passing from agonists to mixed (nalorphine) and pure (naloxone, naltrexone) antagonists. For these latter the observed trend of the internal flexibility about N---C and C---C bonds of the N-substituents is discussed in terms of a correlation with their relative antagonistic potencies. In fact, such an evidence of decreasing internal conformational dynamics in the order nalorphine, naloxone, naltrexone, appeared interestingly in line with the “two-state” model of opiate receptor operation mode proposed by Snyder.     

Theoretical determination of the ionization potentials of the 1σ and 2σ electrons of CO(Σ)

Large-basis-set calculations of near Hartree-Fock accuracy were performed on CO⁺(1σ-hole ²Σ⁺) and CO⁺)2σ-hole, ²Σ⁺); correlation energies for these systems and for CO were calculated using an atoms-in-molecule approach, relativistic energies and vibrational structure corrections were also considered. The results are: IP(CO, 1σ) = 542.4 (542.57) eV, IP(CO,2σ) = 297.0 (296.24) cV, D_c(CO, ¹Σ⁺) = 10.8 (11.1) Ev, D₃(CO⁺, 1σ, ²Σ⁺) = 11.9 eV, D_e(CO⁺, 2σ, ²Σ⁺) = 9.1 eV, where IP and D_e stand respectively for ionization potential and dissociation energy, and where the numbers in parentheses refer to the most recent experimental values. The electron transfers resulting from the ionization of inner-shell electrons are discussed. Finally a quantitative correlation is developed correlating absolute chemical shifts to charge densities. Agreement between the calculated values and those derived from the correlation is quite satisfactory.