The proton relaxation of methyl cyanide in the presence of Ni(II) ions,as studied by spin-echo techniques

The proton relaxation times (T ₁ and T ₂) of methyl cyanide, in the presence of Ni(II) ions, have been measured as a function of temperature and frequency by spin-echo techniques. The observed decay times (T ₂?) have also been measured as a function of the separation, t _ep, between the pulses in a Carr-Purcell train of echos. The results obtained in the limit of long pulse separation have been fitted to existing theories. The rotational correlation time of the Ni/MeCN complex, τ _R , the electron spin relaxation time, τ _S , and the distance of closest approach of the protons to the nickel have been estimated from the results. In addition the scalar coupling constant, the exchange rate τ _B and the activation energies for τ _B , τ _S and τ _R have been evaluated. The chemical exchange parameters obtained differ significantly from those obtained by previous workers. There is evidence from the pulse dependence experiments that the complex is a distorted octahedron.     

Electron spin relaxation in solutions of manganese (II) ions

Measurements of the neutron scattering static structure factor S(Q) are reported for orthobaric liquid fluorine at 77K for an incident wavelength of 1·2Å. The observed S(Q) and the atom-atom correlation function are discussed and compared with those of other halogens and oxygen. From the d(r) pair distribution function it is shown that liquid fluorine has a coordination number of first neighbours more similar to liquid oxygen than halogens. The number of atoms in the first and second coordination shell is in good agreement with a close-packed arrangement of atoms.     

Electron paramagnetic relaxation in aqueous solutions of manganese (II) ions

The processes of the electron paramagnetic relaxation, molecular motions and structural changes in aqueous solutions of manganese nitrate have been investigated by direct measurement of spin-lattice (T ₁) and spin-spin (T ₂) relaxation times for a wide range of concentrations, temperatures and viscosities. T ₁ and T ₂ were measured by a non-resonance absorption method.

It was discovered that some structural regions exist at the different concentrations of Mn(II) ions in solution. So, the structure of highly concentrated solutions may be considered as one of the corresponding crystallohydrate. The structural microinhomogeneities were observed also in the intermediate concentration range at definite temperatures. It is shown that the relaxation mechanism proposed by Bloembergen and Morgan is not effective in the concentration range studied by us.

The analysis of relaxation times and E.P.R. spectra has shown the formation of ‘liquid microphases’ at the freezing point of the solution. Such microphases can exist at temperatures a few tenths of a degree below the solvent freezing point, and its composition considerably differs from the initial solution.

The correlation times for intramolecular and intermolecular electron relaxation mechanisms are evaluated and their nature is discussed.     

Electron spin relaxation of copper(II) ions in diamagnetic crystals

The electron spin-lattice and spin-spin phase relaxation measurements of Cu²⁺ ions in various crystals are reviewed and discussed. Examples of the Debye temperature determination from a wide temperature range measurements of the spin-lattice relaxation time T₁ are shown. An influence of the Jahn-Teller dynamics on T₁ is presented. The phase relaxation described by the phase memory time T_M is affected by temperature due to the spin packet width modulation by molecular motions. The T_M is anisotropic in crystals and can be different for different hyperfine lines of an EPR spectrum.     

Global Fit of Torsion-Rotational Transitions in the First Three Torsional States of CH(3)OD

A global fit of the observed high-resolution microwave (MW), millimeter-wave (MMW), and Fourier transform far-infrared (FIR) spectra for CH(3)OD has been performed using a reduced torsion-rotational Hamiltonian that is obtained from the one-large-amplitude internal-rotation model. The CH(3)OD data set contains 460 MW and MMW transitions with two or fewer quanta in the torsion, v(t) 相似文献   

Millimeter-Wave Spectra and Global Torsion-Rotation Analysis for the CH(3)OD Isotopomer of Methanol

New millimeter-wave and microwave measurements for CH(3)OD have been combined with previous literature data and with an extended body of Fourier transform far-infrared observations in a full global analysis of the first two torsional states (v(t) = 0 and 1) of the ground vibrational state. The fitted CH(3)OD data set contained 564 microwave and millimeter-wave lines and 4664 far-infrared lines, representing the most recent available information in the quantum number ranges J 相似文献   

Spin-spin relaxation in heteropolynuclear clusters containing iron(III) and copper(II) ions

The magnetic coupling between Fe(III) and Cu(II) and the relaxation behavior of the spin centered at the iron have been studied in di- and trinuclear clusters. The experimental spectra have been analyzed in terms of a simple cross-relaxation model. In the strongly coupled trimer the relaxation rates are determined by a Boltzmann factor and a single field- and temperature-independent scaling parameter¹ w ₀, while the weakly coupled dimer exhibits obviously a more complex behavior.     

Barriers to internal rotation and tunnelling splittings of the torsional states in the HO(CH2)OH,DO(CH2)OH and DO(CH2)OD molecules

Torsional states caused by vibrations of hydroxyl groups in the methanediol molecule and its two deuterated analogues – DO(CH₂)OH and DO(CH₂)OD were analysed at MP2/cc-pVTZ and CCSD(T)/cc-pVQZ levels of theory. In the first case, 2D PES and 2D surfaces of kinematic coefficients were calculated with geometry optimisation for all other geometric parameters, and in the second case, only the energy of optimised configurations at the MP2/cc-pVTZ level of theory was determined. Then 2D PES was recounted to the complete basis set (CBS) limit by extrapolating the results of calculations at the MP2/cc-pVTZ and MP2/cc-pVQZ levels of theory The calculated values were then averaged over four equivalent points on the coordinate plane. Hamiltonian matrices were constructed using DVR and Fourier methods. After their subsequent diagonalization, the energies of the stationary torsional states were computed. Their classification by C_2V(M) and C_S(M) molecular symmetry groups has been performed. The splitting values due to the tunnelling of the thirty most deeply located torsional states in the three studied molecules were also determined. The torsional states, internal rotation barriers, and tunnelling frequencies in the molecules of methanediol and hydrogen trioxide were compared.     

Structures of proton solvates in the HCl-H2O-(CH3)2NCHO system as determined by IR spectroscopy and quantum-chemical calculations

The structures of proton solvates in the HCl-H₂O-(CH₃)₂NCHO (DMFA) system at H₂O: DMFA ratios ranging from 1: 1 to 21: 1 are studied by the IR spectroscopy method. It is demonstrated that H₂O?H⁺?OH₂ ions and (CH₃)₂NCHO?H⁺?OH₂ mixed solvates with a strong quasi-symmetrical hydrogen bond are formed in solutions. With an increase in the DMFA concentration, the fraction of H₅O ₂ ⁺ ions decreases. At HCl: H₂O ≥ 1: 3 and arbitrary DMFA concentrations, only mixed proton solvates are formed. The continuous absorption coefficients for the (CH₃)₂NCHO?H⁺?OH₂ ions are determined. The results obtained are compared with the results of quantum-chemical calculations of the structure and relative stability of the (DMFA) _m H⁺(H₂O) _n (m = 0–2, n = 0–3) positively charged complexes which were performed by the B3LYP/6-31++G(d,p) DFT method. We identified 19 stable configurations with chain, cyclic, and branched structures. Most of these configurations contain the (CH₃)₂NCHO?H⁺?OH₂ fragment. The parameters of the O?H⁺?O bridge show that some configurations have a strong quasi-symmetrical hydrogen bond. In some cases, the proton is located between two DMFA molecules. The H₂O?H⁺?OH₂ bridge is observed in none of the stable configurations of the (DMFA) _m H⁺(H₂O) _n (m ≠ 0) complexes.     

Optical properties of the proton conductor (NH2(CH3)2)2CoCl4

Based on the data from optical-spectral studies of (NH₂(CH₃)₂)₂CoCl₄ crystals, the existence of high-temperature phase transitions at 419, 380, 352, and 313 K is confirmed. It was shown that with the exception of the first transition, they are related to a considerable extent to rearrangement of the network of hydrogen bonds and are not accompanied by, considerable deformation of the lattice. In this connection the character of the electron-phonon interaction remains unchanged in the entire temperature range of the measurements. The (NH₂(CH₃)₂)₂CoCl₄ structure at room temperature is close to that of the ordered low-temperature phases of such isomorphous crystals as β-K₂SO₄. I. Franko State University, L’vov, Ukraine, 8, Kirill and Mefodii St., UA-290005, L’vov. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 3, pp. 412–418, May–June, 1998.     

Classical and quantum molecular dynamics of cation in (CH3NH3)3 Sb2Br9 polycrystal as studied by 1H NMR.

¹H spin-lattice relaxation times and second moments were determined for polycrystalline (CH₃NH₃)₃Sb₂Br₉ sample in a wide range of temperature (5–200 K) at 24.6 and 55.2 MHz. ²H NMR spectra of (CD₃NH₃)₃Sb₂Br₉ were recorded between 5 K and room temperature. The relaxation time is interpreted as a result of motion of two different non-equivalent types of monomethylammonium cations occurring at the 2:1 proportion in a unit cell. Below 30 K, the relaxation processes via tunneling are suggested to dominate. Above 30 K, only classical behaviour of methylammonium cations is detected. Two monomethylammonium cations relax with the classical correlated C₃ reorientation and the rotational tunnelling mechanism, while the third cation exhibits only the classical correlated reorientation. The dynamic parameters of these motions have been determined.     

Slow enthalpy relaxation in (KCN)0.7(KBr)0.3 studied by adiabatic calorimetry

Calorimetric measurement on (KCN)_0.7(KBr)_0.3 mixed crystals showed relaxational heat capacity anomalies around 25 K. The temperature-time curves observed under the adiabatic condition were found to follow the Kohlrausch-Williams-Watts equation, indicating non-exponential behavior of the enthalpy relaxation. The phenomena were explained in terms of a frozen-in process of the orientational degrees of freedom of cyanide ions in the low-temperature monoclinic phase.     

Molecular dynamics of amide ions in potassium amide (KNH2) studied with orientation-dependent deuterium spin lattice relaxation

The reorientational molecular dynamics of the amide ions were investigated in three different phases of KND2 by means of 2H NMR line-shape analyses of solid-echo, T1Z as well as T1Q distorted spectra in a temperature range of 80-420 K. The correlation times of the amide dynamics cover roughly eight decades in this temperature range. Due to the nonzero asymmetry parameter (eta approximately 0.2) of the electric field gradient tensor the calculation of the orientation-dependent spectral densities Jm(theta, phi) required for the interpretation of the T1Z and T1Q distorted spectra cannot be simplified as in the case eta = 0 and a numerical approach was used for the calculation of Jm(theta, phi), which allows a maximum flexibility for simulating different models of motion. The amide ion dynamics in the low-temperature phase can be described as a superposition of a thermally activated large angle jump of the amide ions about their two-fold axes in an asymmetric four-well potential and strongly anisotropic molecular librations. The asymmetry of the potential surface of the jump process was found to be a function of temperature. Activation energy EA, attempt frequency tau0(-1) and DND bond angle epsilon were determined to 15.5(2) kJ/mol, 62(6) x 10(12) s(-1) and 104.7(3) degrees. In the middle- and high-temperature phases the amide ions perform 90 degrees jumps about the crystallographic four-fold axes. For the high-temperature modification the correlation times were observed to follow an Arrhenius law with EA = 6.3(2) kJ/mol and tau0(-1) = 32(3) x 10(12) s(-1).     

Acyclic donor-acceptor-donor chromophores for large enhancement of two-photon absorption cross-section in the presence of Mg(II), Ca(II) or Zn(II) ions

Two new chromophores in the format, donor-acceptor-donor, have been synthesized in high yields from easily available starting materials. These compounds do not show any two-photon absorption (TPA) cross-section in the wavelength range, 780-900 nm when probed by the Z-scan technique with a femtosecond laser. However, in presence of Zn(II), Ca(II) or Mg(II) ion, each compound gives exceptionally large TPA cross-section in the same wavelength range.