The microwave spectrum of α-fluoropropionic acid

The rotational absorption lines in the microwave spectrum of α-fluoropropionic acid were shown to originate from two different molecular conformations. The rough geometries of the two conformations could be determined from the observed dipole moments and the substitution coordinates of the carboxylic hydrogen atom. In both conformations the fluorine atom is near the plane of the carboxyl group; in the conformation with the fluorine atom trans with respect to the hydroxyl group the carboxyl group has the usual geometry, while in the cis conformation the molecule is stabilized by an internal OH?F hydrogen bond. By measuring the relative intensities of the absorption lines it was found that the cis conformer is 0.5 ± 0.2 kJ mole^?1 lower in energy than the trans conformer. The barrier to internal rotation of the methyl group in the trans conformation was determined from A-E line splittings in the second excited vibrational state V₃ = 13.5 ± 0.3 kJ mole^?1.     

Barriers to internal rotation in asymmetric molecules: 2,3-Difluoropropene

The potential function for internal rotation in 2,3-difluoropropene has been obtained from the microwave spectrum of the gauche rotamer, the far- and mid-infrared spectra of both the gauche and cis rotamers and the absolute rotational intensity measurements of several gauche microwave transitions. It is found that the cis conformer is most stable by 145 ± 60 cm⁻¹. Both the cis-gauche and gauche(+)-trans-gauche(−) barriers are approximately 1000 cm⁻¹. A comparison between the potentials in 2,3-difluoropropene, propene, and several other fluoropropenes is made. The dipole moment of the gauche conformer is μ_a = 0.950 D, μ_b = 1.982 D, and μ_c = 1.135 D; μ_total = 2.67 D.     

Microwave spectrum and rotational isomerism of n-propyl isocyanide

The microwave spectrum of n-propyl isocyanide has revealed the existence of two rotational isomers, trans (methyl trans to the isocyanide substituent), and gauche. Plausible structures have been fitted to the data, giving the gauche dihedral angle as 119° ± 2° from the trans position. Stark effect measurements have yielded dipole moments for the two rotamers: μ_trans = 4.16 ± 0.02 D and μ_gauche = 4.10 ± 0.09 D. The rotational constants of the trans form are A = 23 700 ± 100, B = 2407.632 ± 0.020, and C = 2278.853 ± 0.030 MHz, and those of the gauche form are A = 10 208.983 ± 0.030, B = 3479.219 ± 0.015, and C = 2859.981 ± 0.015 MHz. It has been found from relative intensity measurements that the gauche ground state is slightly more stable than the trans ground state, with an energy difference of 99 ± 45 cm^?1. Several vibrationally excited states have been assigned to the torsional motion around the central carbon-carbon bond, the CNC bending motion, and the methyl internal rotation. The torsional vibration frequency is 114 ± 20 cm^?1 in the trans form and 123 ± 20 cm^?1 in the gauche form. A four-term potential function for internal rotation about the central CC bond has been determined.     

Microwave spectrum and rotational isomerism in isopropyl mercaptan

A microwave investigation of isopropyl mercaptan has established the existence of both trans and gauche conformers, the trans being more stable by 57 cal mole^?1. Stark effect measurements give the dipole moments as 1.61 ± 0.2 D for the trans and 1.53 ± 0.2 D for the gauche species. The spectra of the isotopic species (CH₃)₂CH³²SD, (CH₃)₂CH³⁴SH, and (CH₃)₂CH³⁴SD of the trans form have also been analyzed, providing a limited amount of structural data.The rotational spectrum of the gauche isomer is noticeably influenced by inversion. Interactions between energy levels in the two lowest inversion states have been satisfactorily accounted for in terms of rotational constants, coupling parameters (G_a and G_c), and ΔE₀, the inversion level splitting. ΔE₀ is found to be 562.4 MHz for the ground state of (CH₃)₂CHSH and 10.0 MHz for (CH₃)₂CHSD. A value of 1.98 kcal mole^?1 has been calculated for the barrier to internal rotation of the -SH group in terms of a V₃ potential.     

Molecular beam reactive scattering of Br2 from Pd(111) using an electrochemical effusive source

A computer-controlled modulated molecular beam source is used to investigate the kinetics of the surface reactions which occur when bromine is reactively scattered by Pd(111). The reaction products are atomic bromine and molecular bromine: the latter species arises from an adatom recombination process and gives rise to a product vector modulated at twice the frequency of the incident beam (2ω.) By making suitable measurements of the temperature dependence of the product vector phase shifts at ω and 2ω, the four kinetic parameters which characterise the first-order and second-order rate processes are obtained. These are: A₁ = 2.5×10⁹ s^?1, E₁ = 177 kJ mol^?1, A₂ = 3.6×10^?10 m² s^?1, E₂ = 131 kJ mol^?1. The significance of these values is discussed in terms of the properties of the transition state to desorption.     

Pulsed NMR study of hydronium β-alumina

Pulsed ¹H NMR measurements are reported for hydronium β-alumina powder in the temperature range 77 K < T < 440 K at 16 MHz. Motional narrowing due to translation (E_A = 21 kJ mol^-1 occurs at T > 260 K. Spin-lattice relaxation is non-exponential in both the laboratory and rotating frames. The observed M₂ suggests that reorientation of H₃O⁺ may also occur, but there are no indications of reorientational minima in T₁ or T_1?.     

垂直排列液晶盒中反铁电液晶TFMHxPOCBC-D2偏振红外光谱研究

本文通过偏振红外吸收光谱研究了铁电与反铁电液晶分子TFMHxPOCBC-D₂(4-(trifluoromethylhexy-3-d₂ carbonyl)phenyl 4′-octyloxybiphenyl caboxylate)在垂直排列取向液晶盒中CD₂基团绕手征性烷基链转动的受阻行为.实验结果显示CD₂的偏振红外吸收在Sm-C相不同于Sm-C_A相.建立了一个CD₂转动受阻模型,在这一模型的基础上,对CD₂的偏振红外吸收进行了模拟计算,较好地解释了CD₂红外吸收在铁电和反铁电液晶相下的行为差异,得到了CD₂基团绕手征性烷基链转动受阻的结论. 关键词： 反铁电液晶 红外光谱 受阻转动     

Dynamical structure of peptide molecules: Fourier transform microwave spectroscopy of N-methylpropionamide

In order to clarify the dynamical aspects of the peptide structure, N-methylpropionamide (NMPA) was investigated as an example of peptide molecules: XCONHY (X=CH₃CH₂ and Y=CH₃ for NMPA), paying special attention to the internal rotation of the two methyl groups. NMPA was found to have an almost planar skeleton with an extended syn/trans conformation, as indicated by the observed value of I_aa+I_bb−I_cc, and its rotational spectra were interpreted in terms of group G₁₈ consisting of six symmetry species: A₁, A₂, E₁, E₂, E₃, and E₄. The A₁ and E₂ spectra were observed split in most of b-type transitions, yielding the internal-rotation potential barrier V₃ of 796 (21) cm⁻¹ for CH₃ in the ethyl group referred to as C-CH₃. The spectra of the three E species: E₁, E₃, and E₄ appeared several tens to thousands MHz apart from the corresponding A₁ spectra, suggesting the internal-rotation potential barrier of CH₃ bonded to the nitrogen, called N-CH₃, to be quite low. In sharp contrast with the A₁ spectra, which were well fitted to the ordinary asymmetric-rotor spectral pattern, a few higher-order terms were required to reproduce the E₁ spectra, presumably because of the low N-CH₃ barrier. The spectral analysis thus performed, in fact, led to the V₃ of 80.06487 (14) cm⁻¹, an order of magnitude lower than that of C-CH₃. The E₃ and E₄ spectra were found to form triplets with the corresponding E₁ lines at the center, and the E₃-E₁ and E₄-E₁ splittings were explained essentially by the contributions of the C-CH₃ internal rotation combined with the kinetic-energy coupling between the two methyl groups. The torsion around the C-C bond between the ethyl and carbonyl groups was suggested by an ab initio calculation to be of double minimum nature, but the observed A₁ spectra did not show any indication of such a double-minimum potential for the C-C torsion, although the possibility of a small hump being present at a planar conformation could not be entirely eliminated. The present results on NMPA along with those obtained on other peptide molecules will be of some significance in clarifying important problems of structural biology such as protein folding and signal transfer through biological systems.     

Microwave spectra and barriers to internal rotation of trifluoroacetic acid and trifluoroacetyl fluoride

The rotational transitions of trifluoroacetic acid and trifluoroacetyl fluoride were identified with radiofrequency-microwave and microwave-microwave double resonance spectroscopy. Isotopic substitution of the hydrogen atom in trifluoroacetic acid showed that the hydrogen atom is cis with respect to the CO bond. A second conformation was not found. From A,E splittings in higher vibrational levels the internal rotation barriers were calculated: for trifluoroacetic acid, V₃ = 241.8 ± 0.5 cm^?1 (v = 4); for trifluoroacetyl fluoride V₃ = 383.6 ± 0.5 cm^?1 (v = 5).     

The microwave spectrum and conformations of halomethyl oxiranes: Bromomethyl oxirane

The microwave spectrum of bromomethyl oxirane

has been recorded in the range 12.5–18 and 26.5–40 GHz. Lines of the two bromine isotopic species of three rotamers, gauche-1 (Br near the O atom), gauche-2 (Br near the CH₂ of the ring) and cis have been identified. The gauche-1 lines are strongest, and the cis lines the weakest. The rotational constants (in MHz) are: gauche-1 (⁷⁹Br) A = 12 296.050, B = 1 391.677, C = 1 317.360, (⁸¹Br) A = 12 199.162, B = 1 378.321, C = 1 309.142; gauche-2 (⁷⁹Br) A = 12 278.436, B = 1 378.830, C = 1 304.852, (⁸¹Br) A = 12 189.869, B = 1 369.696, C = 1 301.584; cis (⁷⁹Br) A = 7 733.314, B = 1 808.087, C = 1 737.340, (⁸¹Br) A = 7 726.16, B = 1 801.159, C = 1 730.125.     

On the existence of condensed phases in low-dimensional systems

It is shown that the threshold interaction constant (TIC) α_D for the existence of a condensed phase increases with the dimension D of a Bose system (α₃ < α₂ < α₁). TICs are evaluated exactly for a wide class of two-parameter potentials (the latter may approximate real physical interactions). The results are applied to spin-polarized systems. The possibility of an electric field induced liquid-gas transition is discussed. The TIC for N-particle clusters diminishes with N.     

NMR study of protonic transport in hydronium beta″ alumina

NMR relaxation time measurements have been made at 20 MHz for proton in polycrystalline hydronium beta″ alumina. Motional narrowing occurs at T > 62;230 K(E_a = 19 kJ mol^?1) in the fully hydrated beta″ alumina and the relaxation behavior is compatible with fast proton transport. The protonic motion in the partially dehydrated beta″ alumina has a high activation energy as 24.5 kJ mol^?1.     

The microwave spectrum of difluoroacetic acid

Transitions due to two conformations have been observed in the microwave spectrum of difluoroacetic acid. In both rotamers the carboxylic hydrogen atom is cis to the CO bond, whereas the other hydrogen atom is either trans or gauche with respect to the CO bond. By means of isotopic substitution of the hydrogen and oxygen atoms a serious deviation of local symmetry in the CHF₂ group is deduced for the gauche form. This is thought to be an artifact of the substitution method, although no satisfactory explanation can be given. In torsionally excited states of the gauche conformation, doublet splittings were observed due to tunneling through a barrier of 190 ± 10 cm^?1. For the second excited state a satisfactory treatment could be given, but for the third excited state large differences between observed and calculated transition frequencies remained. A computer program to account for the internal rotation in asymmetric molecules was written, and it was shown qualitatively that interactions with excited states of the trans conformation could very well be responsible for the discrepancies. From intensity measurements the energy difference E(gauche) - E(trans) was found to be 370 ± 180 cm^?1. The large uncertainty is due to the failure of attempts to determine the dipole moments experimentally; they were estimated from an improved set of bond moments which was derived from related compounds. Both energy difference and dihedral angles are at variance with the results of an earlier electron diffraction investigation.     

Investigation of H+ motion in the 21-hydrates of 12-tungstophosphoric and 12-molybdophosphoric acids by ac conductivity and pulsed 1H NMR measurements

AC conductivity and ¹H NMR relaxation time measurements are reported for the heteropolyacids H₃PM₁₂O₄₀. 21H₂O (M = W, Mo) over a range of tempereatures.Ambient temperature proton conductivites are ? 1 S m^-1, with conductivity activation energies E ? 40 kJ mol^-1.The NMR results are interpreted in terms of a range of motional processes leading to distributions of translational correlation times. The behaviour is compared to motions in zeolites and of water sorbed by charcoal.     

Motional averaging in an excited state of ZnS: Cu2+

The single isotropic g factor found in the ²E excited state of ZnS:Cu²⁺ is hard to reconcile with the properties of this state, in particular with the moderate strength of the E ? ? vibronic coupling. A vibronic coupling between this state and the vibronic levels of the ground ²T₂ state due to τ₂ modes can bring about motional averaging between strain split states of ²E through a two phonon non-resonant process. In general, excited state mechanisms will be effective between states of the same spin multiplicity and which have large Stoke shifts.     

Microwave spectrum of chloromethyl methyl ether

The microwave spectrum of chloromethyl methyl ether has been studied in the region 12.4–40 GHz. For ³⁵Cl species, a- and c-type transitions have been assigned for the ground state, the first excited state of the chloromethyl torsional mode, and the first excited state of the methyl torsional mode. Assignments were also made for the ground state of ³⁷Cl species. The assigned transitions are due to the gauche conformer. The nuclear quadrupole coupling constants were determined for the ground state of ³⁵Cl and ³⁷Cl species. The observed A-E splittings of the rotational transitions arising from the three vibrational states indicate a strong coupling between the two torsional vibrations. A model calculation based on the Hamiltonian previously used by Butcher and Wilson (J. Chem. Phys.40, 1671 (1964)), was carried out to account for the splittings and the vibrational frequencies of the two torsional modes. The barrier to internal rotation of the methyl group is estimated to be V₃ = 647 ± 17 cm^?1 (1.84 ± 0.05 kcal/mole).     

Li+ transport in Li0.40MoO3 studied by pulse NMR

Pulsed ⁷Li NMR relaxation time measurements are reported for the intercalate Li_0.40MoO₃ in the temperature range 200K < T < 460K at 20 MHz. Temperature dependences of T₁ and T₂ indicate translation of Li⁺ with E_A = 23 kJ mol^-1. The data lead to an estimate for the Li⁺ self-diffusion coefficient at 300K of D¹_300K ? 4 x 10^-12 cm² sec^-1.     

Evidence of the weakness of the OH⋯F hydrogen bond from a conformational study of 3-fluoro-1-propanol by microwave spectroscopy

The rotational spectra of the OH and OD isotopic species have been observed for three rotamers of 3-fluoro-1-propanol. One of them (HBC form) displays an internal hydrogen bond with a distorted chair conformation of the six-membered ring. The other two rotamers have the oxygen atom gauche with respect to the C₂C₃ bond, the hydroxyl hydrogen trans with respect to the C₁C₂ bond and the fluorine atom gauche (GGT form) and trans (TGT form), respectively, with respect to the C₂C₁ bond. The energies of the vibrational ground states of the HBC and TGT forms are ～0.4 and 1.0 kcal/mole higher than that of the GGT form, respectively (from relative intensity measurements). The hydrogen bond is therefore rather weak in this compound. With compounds capable of forming OH?O or OH?N bonds, the conformation appropriate for hydrogen bonding is normally the most stable form. Several excited states have been analyzed for the TGT and GGT rotamers in order to have additional data with respect to the potential function for the internal rotation about the C₃C₂ bond.     

Internal rotation in methyl silane by avoided-crossing molecular-beam spectroscopy

The avoided-crossing molecular-beam electric-resonance technique was applied to methyl silane in the ground torsional state. A new type of anticrossing is introduced which breaks the torsional symmetry and obeys the selection rules ΔJ = 0, K = +1 /a3 ?1. For these “barrier” anticrossings, the values of the crossing fields E_c yield directly the internal rotation splittings; the E_c are independent of the difference (A-B) in the rotational constants. Such anticrossings were observed for J from 1 to 6. Studies were also conducted of several “rotational” anticrossings (J, K) = (1, ±1) /a3 (2, 0) for which E_c does depend on (A-B). The normal rotational transition (J, K) = (1, 0) ← (0, 0) was observed in the ground torsional state using the molecular beam spectrometer. The present data on CH₃²⁸SiH₃ were combined with Hirota's microwave spectra and analyzed with the torsion-rotation Hamiltonian including all quartic centrifugal distortion terms. In addition to evaluating B and several distortion constants, determinations were made of the moment of inertia of the methyl top I_α = 3.165(5) amu-Ų, the effective rotational constant A^eff = 56 189.449(32) MHz, and the effective height of the threefold barrier to internal rotation V₃^eff = 592.3359(73) cm^?1. The correlations leading to these two effective constants are discussed and the true values of A and V₃ are determined within certain approximations. For the isotopic species CH₃³⁰SiH₃, barrier and rotational anticrossings were observed. The isotopic changes in A and V₃ were determined, as well as an upper limit to the corresponding change in I_α.     

2H nuclear magnetic resonance study of deuterated water dynamics in perfluorosulfonic acid ionomer Nafion

We have employed deuteron nuclear magnetic resonance (NMR) spectroscopy in order to study the dynamics of the deuterated water (D₂O) molecules introduced into a perfluorosulfonic acid ionomer Nafion (NR-211) film. According to the ²H NMR spectral analysis, the deuterated water molecules at low temperatures occupied either relatively rigid or mobile sites up to the temperature T_M=240 K where all the deuterated water molecules became mobile. The temperature-dependent NMR linewidths sensitively reflected the motional narrowing of the rigid and mobile sites, and the NMR chemical shift reflected significant changes in the hydrogen bonds of the deuterated water. While a slow- to fast-limit motional transition was manifested at T_M in the laboratory-frame NMR spin–lattice relaxation, the rotating-frame spin–lattice relaxation indicated no bulk liquid water state down to 200 K.