NMR spectra of oriented biologically important molecules - The structure of and the internal rotation in N,N'-dimethyluracil

From the proton NMR spectra of Nfl-dimethyluracil oriented in two different nematic solvents, the internal rotation of the methyl groups about the N-C bonds is studied. It has been observed that the preferred conformation of the methyl group having one carbonyl in the vicinity is the one where a C-H bond is in the ring plane pointing toward the carbonyl group. The results are not sensitive to the mode of rotation of the other methyl group. These data are interpreted in terms of the bond polarizations.

Nuclear Magnetic-Resonance Spectra Of Oriented Biologically Important Molecules - The Structure Of And The Internal-Rotation In N,N-Dimethyluracil

From the proton NMR spectra of Nfl-dimethyluracil oriented in two different nematic solvents, the internal rotation of the methyl groups about the N-C bonds is studied. It has been observed that the preferred conformation of the methyl group having one carbonyl in the vicinity is the one where a C-H bond is in the ring plane pointing toward the carbonyl group. The results are not sensitive to the mode of rotation of the other methyl group. These data are interpreted in terms of the bond polarizations.

Internal rotation in dimethylacetylene

The vibrational spectrum of dimethyl acetylene has been remeasured with better resolving power than hitherto, and the rotational fine structure of some perpendicular type bands has been partly analyzed. The energy levels of a molecule of this kind in which internal rotation of methyl groups may arise have been re-examined theoretically and the rotational structure of the absorption bands has been more clearly defined than previously. The experimental results are consistent with the assumption of unrestricted internal rotation of the methyl groups, and the Coriolis factors $\zeta _{i}$ for several vibrations have been determined.

Solar dynamo models with realistic internal rotation

Solar dynamo models based on differential rotation inferred from helioseismology tend to produce rather strong magnetic activity at high solar latitudes, in contrast to the observed fact that sunspots appear at low latitudes. We show that a meridional circulation penetrating below the tachocline can solve this problem.

I. Nuclear spin-internal-rotation-coupling. II. Fluorine spin-rotation interaction and magnetic shielding in fluorobenzene

Part I.

The interaction of a nuclear magnetic moment situated on an internal top with the magnetic fields produced by the internal as well as overall molecular rotation has been derived following the method of Van Vleck for the spin-rotation interaction in rigid molecules. It is shown that the Hamiltonian for this problem may be written

H_SR = Ῑ · M · Ĵ + Ῑ · M” · Ĵ”

Where the first term is the ordinary spin-rotation interaction and the second term arises from the spin-internal-rotation coupling.

The F¹⁹ nuclear spin-lattice relaxation time (T₁) of benzotrifluoride and several chemically substituted benzotrifluorides, have been measured both neat and in solution, at room temperature by pulsed nuclear magnetic resonance. From these experimental results it is concluded that in benzotrifluoride the internal rotation is crucial to the spin relaxation of the fluorines and that the dominant relaxation mechanism is the fluctuating spin-internal-rotation interaction.

Part II.

The radiofrequency spectrum corresponding to the reorientation of the F¹⁹ nuclear moment in flurobenzene has been studied by the molecular beam magnetic resonance method. A molecular beam apparatus with an electron bombardment detector was used in the experiments. The F¹⁹ resonance is a composite spectrum with contributions from many rotational states and is not resolved. A detailed analysis of the resonance line shape and width by the method of moments led to the following diagonal components of the fluorine spin-rotational tensor in the principal inertial axis system of the molecule:

F/Caa = -1.0 ± 0.5 kHz

F/Cbb = -2.7 ± 0.2 kHz

F/Ccc = -1.9 ± 0.1 kHz

From these interaction constants, the paramagnetic contribution to the F¹⁹ nuclear shielding in C₆H₅F was determined to be -284 ± ppm. It was further concluded that the F¹⁹ nucleus in this molecule is more shielded when the applied magnetic field is directed along the C-F bond axis. The anisotropy of the magnetic shielding tensor, σ_” - σ_⊥, is +160 ± 30 ppm.

The effect of counterpoise correction and relaxation energy term to the internal rotation barriers: application to the BF3 ...NH3 and C2H4 ...SO2 dimers

The relevance of the fragment relaxation energy term and the effect of the basis set superposition error on the geometry of the BF3⋯NH3 and C2H4⋯SO2 van der Waals dimers have been analyzed. Second-order Møller-Plesset perturbation theory calculations with the d95(d,p) basis set have been used to calculate the counterpoise-corrected barrier height for the internal rotations. These barriers have been obtained by relocating the stationary points on the counterpoise-corrected potential energy surface of the processes involved. The fragment relaxation energy can have a large influence on both the intermolecular parameters and barrier height. The counterpoise correction has proved to be important for these systems

On the use of rotational splitting asymmetries to probe the internal rotation profile of stars: Application to beta Cephei stars

Rotationally-split modes can provide valuable information about the internal rotation profile of stars. This has been used for years to infer the internal rotation behavior of the Sun. The present work discusses the potential additional information that rotationally splitting asymmetries may provide when studying the internal rotation profile of stars. We present here some preliminary results of a method, currently under development, which intends: 1) to understand the variation of the rotational splitting asymmetries in terms of physical processes acting on the angular momentum distribution in the stellar interior, and 2) how this information can be used to better constrain the internal rotation profile of the stars. The accomplishment of these two objectives should allow us to better use asteroseismology as a test-bench of the different theories describing the angular momentum distribution and evolution in the stellar interiors. (C) 2010 WILEY-VCH Verlag GmbH&Co. KGaA, Weinheim

An examination chair to measure internal rotation of the hip in routine settings: a validation study

OBJECTIVE: To determine the performance of a newly developed examination chair as compared with the clinical standard of assessing internal rotation (IR) of the flexed hip with a goniometer. METHODS: The examination chair allowed measurement of IR in a sitting position simultaneously in both hips, with hips and knees flexed 90 degrees, lower legs hanging unsupported and a standardized load of 5 kg applied to both ankles using a bilateral pulley system. Clinical assessment of IR was performed in supine position with hips and knees flexed 90 degrees using a goniometer. Within the framework of a population-based inception cohort study, we calculated inter-observer agreement in two samples of 84 and 64 consecutive, unselected young asymptomatic males using intra-class correlation coefficients (ICC) and determined the correlation between IR assessed with examination chair and clinical assessment. RESULTS: Inter-observer agreement was excellent for the examination chair (ICC right hip, 0.92, 95% confidence interval [CI] 0.89-0.95; ICC left hip, 0.90, 95% CI 0.86-0.94), and considerably higher than that seen with clinical assessment (ICC right hip, 0.65, 95% CI 0.49-0.77; ICC left hip, 0.69, 95% CI 0.54-0.80, P for difference in ICC between examination chair and clinical assessment

Photoelectron spectroscopic study of the oxyallyl diradical

The photoelectron spectrum of the oxyallyl (OXA) radical anion has been measured. The radical anion has been generated in the reaction of the atomic oxygen radical anion (O center dot-) with acetone. Three low-lying electronic states of OXA have been observed in the spectrum. Electronic structure calculations have been performed for the triplet states (B-3(2) and B-3(1)) of OXA and the ground doublet state ((2)A(2)) of the radical anion using density, functional theory (DFT). Spectral simulations have been carried out for the triplet statics based on the results of the DFT calculations. The simulation identifies a vibrational progression of the CCC bending mode of the B-3(2) state of OXA in the lower electron binding energy (eBE) portion of the spectrum. On top of the B-3(2) feature, however, the experimental spectrum exhibits additional photoelectron peaks whose angular distribution is distinct from that for the vibronic peaks of the B-3(2) state. Complete active space self-consistent field (CASSCF) method and second-order perturbation theory based on the CASSCF wave function (CASPT2) have been employed to study the lowest singlet state ((1)A(1)) of OXA. The simulation based on the results of these electronic structure calculations establishes that the overlapping peaks represent the vibrational ground level of the (1)A(1) state and its vibrational progression of the CO stretching mode. The A, state is the lowest electronic state of,OXA, and the electron affinity (EA) of OXA is 1.940 +/- 0.010 eV. The B-3(2) state is the first excited state with an electronic term energy of 55 +/- 2 meV. The widths of the vibronic peaks of the (X) over tilde (1)A(1) state are much broader than those of the (a) over tilde B-3(2) state, implying that the (1)A(1) state is indeed a transition state. The CASSCF and CASPT2 calculations suggest that the (1)A(1) state is at a potential maximum along the nuclear coordinate representing disrotatory motion of the two methylene groups, which leads to three-membered-ring formation, i.e., cydopropanone. The simulation of (b) over tilde B-3(1) OXA reproduces the higher eBE portion of the spectrum very well. The term energy of the B-3(1) state is 0.883 +/- 0.012 eV. Photoelectron spectroscopic measurements have also been conducted for the other ion products of the O center dot- reaction with acetone. The photoelectron imaging spectrum of the acetylcarbene (AC) radical anion exhibits a broad, structureless feature, which is assigned to the (X) over tilde (3)A '' state of AC. The ground ((2)A '') and first excited ((2)A') states of the 1-methylvinoxy (1-MVO) radical have been observed in the photoelectron spectrum of the 1-MVO ion, and their vibronic structure has been analyzed.

An analysis of the methyl rotation dynamics in the So (x' A) and T (a A) states of thioacetaldehyde from Pyrolysis jet spectra /

Jet-cooled, laser-induced phosphorescence excitation spectra (LIP) of thioacetaldehyde CH3CHS, CH3CDS, CD3CHS and CD3CDS have been observed over the region 15800 - 17300 cm"^ in a continuous pyrolysis jet. The vibronic band structure of the singlet-triplet n -* n* transition were attributed to the strong coupling of the methyl torsion and aldehydic hydrogen wagging modes . The vibronic peaks have been assigned in terms of two upper electronic state (T^) vibrations; the methyl torsion mode v^g, and the aldehydic hydrogen wagging mode v^^. The electronic origin O^a^ is unequivocally assigned as follows: CH3CHS (16294.9 cm"'' ), CH3CDS (16360.9 cm"'' ), CD3CHS (16299.7 cm"^ ), and CD3CDS (16367.2 cm"'' ). To obtain structural and dynamical information about the two electronic states, potential surfaces V(e,a) for the 6 (methyl torsion) and a (hydrogen wagging) motions were generated by ab initio quantum mechanical calculations with a 6-3 IG* basis in which the structural parameters were fully relaxed. The kinetic energy coefficients BQ(a,e) , B^(a,G) , and the cross coupling term B^(a,e) , were accurately represented as functions of the two active coordinates, a and 9. The calculations reveal that the molecule adopts an eclipsed conformation for the lower Sq electronic state (a=0°,e=0"') with a barrier height to internal rotation of 541.5 cm"^ which is to be compared to 549.8 cm"^ obtained from the microwave experiment. The conformation of the upper T^ electronic state was found to be staggered (a=24 . 68° ,e=-45. 66° ) . The saddle point in the path traced out by the aldehyde wagging motion was calculated to be 175 cm"^ above the equilibrium configuration. The corresponding maxima in the path taken by methyl torsion was found to be 322 cm'\ The small amplitude normal vibrational modes were also calculated to aid in the assignment of the spectra. Torsional-wagging energy manifolds for the two states were derived from the Hamiltonian H(a,e) which was solved variationally using an extended two dimensional Fourier expansion as a basis set. A torsionalinversion band spectrum was derived from the calculated energy levels and Franck-Condon factors, and was compared with the experimental supersonic-jet spectra. Most of the anomalies which were associated with the interpretation of the observed spectrum could be accounted for by the band profiles derived from ab initio SCF calculations. A model describing the jet spectra was derived by scaling the ab initio potential functions. The global least squares fitting generates a triplet state potential which has a minimum at (a=22.38° ,e=-41.08°) . The flatter potential in the scaled model yielded excellent agreement between the observed and calculated frequency intervals.

Ab initio studies of the structure and vibrational spectra of methyl isocyanide-borane and acetonitrile-borane

The SCF/DZP and MP2/DZP methods of ab initio quantum chemistry have been utilized to study the structure, vibrational spectra, binding energy, and barrier to internal rotation of methyl isocyanide-borane and acetonitrile-borane adducts. The eclipsed conformation of the complexes was predicted to be a minimum, and the staggered form is a transition state with a barrier height of about 10 cal/mol. The vibrational analyses of CH3NC-BH3 and CH3CN-BH3 and several of their isotopomers have been carried out by the GF matrix method. Computations have also been carried out for free CH3NC and CH3CN in order to investigate the changes in CH3NC and CH3CN as a result of their complex formation with BH3. To obtain an acceptable set of force constants, a recently proposed procedure ''RECOVES'' has been utilized. The increase in the N=C/C=N stretching force constant of CH3NC/CH3CN on adduct formation is interpreted with the help of Parr and Borkman's model. The binding energies for the two adducts have been determined taking basis set superposition error (BSSE) into consideration. The effect of the BSSE on structure, dipole moment, and vibrational frequencies of CH3CN and CH3NC is also evaluated. The predicted infrared band intensities for the two complexes are in good agreement with the experimentally observed features, and they have been utilized in the assignment of vibrational frequencies.

Ultrafast excited state dynamics controlling photochemical isomerization of N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium coordinated to a {Re-1(CO)(3)(2,2 '-bipyridine)} chromophore

Two Multifunctional photoactive complexes [Re(Cl)(CO)(3)-(MeDpe(+))(2)](2+) and [Re(MeDpe(+))(CO)(3)(bpy)](2+) (MeDpe(+) = N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium, bpy = 2,2'-bipyridine) were synthesized. characterized. and their redox and photonic properties were investigated by cyclic voltammetry: ultraviolet-visible-infrared (UV/Vis/IR) spectroelectrochemistry, stationary UV/Vis and resonance Raman spectroscopy; photolysis; picosecond time-resolved absorption spectroscopy in the visible and infrared regions: and time-resolved resonance Raman spectroscopy. The first reduction step of either complex Occurs at about -1.1 V versus Fc/Fc(+) and is localized at MeDpe(+). Reduction alone does not induce a trans -> cis isomerization of MeDpe(+). [Re(Cl)(CO)(3)(MeDPe(+))(2)](2+) is photostable, while [Re(MeDpe(+))(CO)(3)(bpy)](2+) and free MeDpe(+) isomerize under near-UV irradiation. The lowest excited state of [Re(Cl)(CO)(3)(MeDPe(+))(2)](2+) has been identified as the Re(Cl)(CO)(3) -> MeDpe(+) (MLCT)-M-3 (MLCT = metal-to-ligand charge transfer), decaying directly to the ground state with lifetimes of approximate to 42 (73%) and approximate to 430ps (27%). Optical excitation of [Re(MeDpe(+))(CO)(3)(bpy)](2+) leads to population of Re(CO)(3) -> MeDpe(+) and Re(CO)(3) -> bpy (MLCT)-M-3 states, from which a MeDpe(+) localized intraligand 3 pi pi* excited state ((IL)-I-3) is populated with lifetimes of approximate to 0.6 and approximate to 10 ps, respectively. The 3IL state undergoes a approximate to 21 ps internal rotation, which eventually produces the cis isomer on a much longer timescale. The different excited-state behavior of the two complexes and the absence of thermodynamically favorable interligand electron transfer in excited [Re(MeDpe(+))(CO)(3)(bpy)](2+) reflect the fine energetic balance between excited states of different orbital origin, which can be tuned by subtle Structural variations. The complex [Re(MeDpe+)(CO)(3)(bpy)](2+) emerges as a prototypical, multifunctional species with complementary redox and photonic behavior.

Highly correlated ab initio study of the far infrared spectra of methyl acetate

Highly correlated ab initio calculations (CCSD(T)) are used to compute gas phase spectroscopic parameters of three isotopologues of the methyl acetate (CH3COOCH3, CD3COOCH3, and CH3COOCD3), searching to help experimental assignments and astrophysical detections. The molecule shows two conformers cis and trans separated by a barrier of 4457 cm−1. The potential energy surface presents 18 minima that intertransform through three internal rotation motions. To analyze the far infrared spectrum at low temperatures, a three-dimensional Hamiltonian is solved variationally. The two methyl torsion barriers are calculated to be 99.2 cm−1 (C–CH3) and 413.1 cm−1 (O–CH3), for the cis-conformer. The three fundamental torsional band centers of CH3COOCH3 are predicted to lie at 63.7 cm−1 (C–CH3), 136.1 cm−1 (O–CH3), and 175.8 cm−1 (C–O torsion) providing torsional state separations. For the 27 vibrational modes, anharmonic fundamentals and rovibrational parameters are provided. Computed parameters are compared with those fitted using experimental data.

Simulation of glassy state relaxations in polymers: A static analysis of methyl group and methoxy group rotation in poly(vinyl methyl ether)

We show that the simple quasi-static technique, also called the adiabatic mapping technique, can be used to determine the energetics of rotation of methyl and methoxy groups in amorphous poly(vinyl methyl ether) even though the latter process is too slow to be amenable to direct molecular dynamics simulation. For the methyl group rotation, we find that the mean and standard deviation of the simulated rotational barrier heights agree well with experimental data from quasi-elastic neutron scattering. In the case of the methoxy groups we find that just 4% of the groups contribute more than 90% of the observed dielectric relaxation strength. The groups which make the most contribution are those which, by virtue of their particular conformation and local environment, have two alternative positions of similar energy.