Effects of concentration and temperature on molar volumes of L-serine, L-isoleucine, and L-glutamine in aqueous NaCl and NaNO3 solutions

Densities of L-serine, L-isoleucine, L-glutamine in 1.5 mol kg^?1 aqueous NaCl, and NaNO₃ solutions have been measured for several molal concentrations of amino acids at temperatures from 298.15 to 323.15 K. The partial molar volumes (? _v ⁰ ) of L-serine, L-isoleucine, and L-glutamine in 1.5 mol kg^?1 aqueous NaCl/NaNO₃ solutions have been computed using density data. The transfer partial molar volumes (Δ_tr? _v ⁰ ) of L-serine, L-isoleucine, and L-glutamine from water to 1.5 mol kg^?1 aqueous NaCl/1.5 mol kg^?1 aqueous NaNO₃ solutions have been determined at 298.15 K. The trends of variation of ? _v ⁰ and Δ_tr? _v ⁰ with change in temperature have been discussed in terms of ion-ion, ion-hydrophilic, and ion-hydrophobic interactions operative in solutions.     

Low temperature vibrational relaxation of carbon monoxide by light mass species

The rates of deactivation of CO(v=1) by ⁴He and by ³He have been measured between 300 K and 80 K using a pulsed laser fluorescence technique. The results show the usual strong deviation from Landau—Teller behaviour and a marked isotope effect. Comparison is made with theoretical predictions including a one-dimensional treatment which takes account of attractive forces. The present results are compared also with earlier work on the deactivation of CO by H₂, HD and D₂. It has been found that at and below 300 K D₂ is less efficient than ⁴He in the (VT) deactivation of CO (v=1) and HD is anomalously efficient. The latter effect is attributed to the involvement of rotational transitions.     

Quasi-resonant energy transfer in collisions: Na2(A1Σ u + )+K(4S)

Cross sections for electron energy transfer from the initial rotational stateJ′of the two lowest vibrational levelsv′=0 andv′=1 of excited dimers Na₂(A) to potassium atoms as described by Na₂(A¹Σ _u ⁺ ,v′J′)+K(4S)→Na₂ (X¹Σ _g ⁺ ,v″J″)+K(4P)+ΔE have been examined by laser-induced fluorescence. A strong increase of the cross section by as much as an order of magnitude has been observed for those dimerv′J′-levels for which the dipole transitions are close to resonance of the 4S-4P transitions in the atom (ΔE<4 cm^?1). The absolute cross sections for energy transfer have been calculated by the Rabitz approximation of first-order perturbation theory. In the case of closest energy resonance (ΔE=0.9 cm^?1) the cross section is Q=7.8×10^?13 cm².     

Hydrogen bonding: Part IX. Low temperature infrared spectra of H4O2F22− and H6O42− cluster anions in tetramethylammonium fluoride and hyd

At 10–20 K the broad room temperature IR bands of the hydrogen bonded cluster anions in tetramethylammonium fluoride and hydroxide monohydrates and monohydrates-d_n are resolved into a number of components. The band patterns are consonant with distortion of formally tetrahedral H₄F₂O₂^2? and H₆O₄^2? ions of T_d point group to C2v and S₄, respectively in a C_4h⁵ unit cell isomorphous with tetramethylammonium hexafluorosilicate. A lattice mode has been identified for each monohydrate.     

O-H and O-D stretching vibrations in isotopically dilute HDO molecules in some solid hydrates

Vibrational frequencies v_OH and v_OD have been measured for isotopically-dilute HDO molecules in eleven solid hydrates at 90 K. The results have been used to prepare a plot of the ratio v_OH/v_OD versus v_OH. The ratios fall on a smooth curve and decrease with decreasing frequencies v_OH. The anharmonicity constants ω_ex_e have been estimated. They were found to increase with decreasing v_OH.     

Inelastic neutron scattering spectra of alkali metal (Na,K) bifluorides: The harmonic overtone of v3

Inelastic neutron scattering spectra of MFHF (M  Na and K) have been measured up to energy transfers of ca. 4000 cm^?1 Both 0 → 1 and 0 → 2 transitions of the bending (v₂), and antisymmetric stretching (v₃) modes were observed. A normal harmonic (i.e. no quartic contribution) model for the dynamics of the bifluoride ion is entirely consistent with our observations. Evidence of phonon dispersion was observed in the band shape of v₃, but no structure attributable to the LO mode could be found. The similarity of the band shapes of v₃ for both NaFHF and KFHF is interpreted in terms of a very short range coupling mechanism.     

Normal modes of the MoO2−4 ion in Tb1.8Eu0.2(MoO4)3 single crystal

Polarized Raman spectra (single crystal) at 300 K and infrared spectra (powder) at 300 and 77 K in the region 250–1000 cm^?1 of a binary molybdate of terbium and europium have been recorded. Based on C_2v symmetry, group theoretical analysis has been carried out and a vibrational assignment is proposed.     

Dipole moment derivatives for SO2

Dipole moment derivatives for the vibration-rotation fundamentals v₁, v₂, and v₃ of ³²S¹⁶O₂ have been computed to have the mean absolute values 60.5, 63.6, and 165.9 esu G^?1/2, respectively. These results include remeasured band intensities for v₁ and v₂.     

Picosecond study of singlet exciton dynamics in polyvinylcarbazole (PVK) in the temperature range 5–300 K

Rise and decay of spectrally resolved fluorescence of PVK have been measured between 5 and 300 K at a 10 ps time resolution. Build-up of the trap emission near 420 nm is non-exponential. It indicates that transfer of singlet excitons is a time-dependent (dispersive) process reflecting the spread of the energies of the hopping sites. Experimental build-up functions are recovered on the premises that the rate constant for exciton transfer follows v(t) = v_o(t/t_o)^a?1. The dispersion parameter varies between α = 0.2±0.05 at T ?40 K and α = 0.8 at T = 150 K as predicted by computer simulations.     

Vibrational energy transfer in CH3I

Previous works have reported vibration—vibration and vibration—translation transfer rates in the methyl halides. Using the technique of laser induced infrared fluorescence we have studied energy transfer in the concluding member of this series, CH₃I. Following excitation by resonant lines of a Q-switch CO₂ laser, infrared fluorescence has been observed from the v₂, v₅ as well as the 2v₅, v₁, v₄ vibrational energy levels of CH₃I. All the observed states exhibit a single exponential decay rate of 23 ± 2 ms^?1 torr^?1. Measurements have also been made on deactivation of the various modes by rare gases. The risetime of the v₂, v₅ levels was found to be approximately 101 ± 20 ms^?1 torr^?1, while that of the 2v₅, v₁, v₄ levels was approximately 225 ± 45 ms^?1 torr^?1. Fluorescence was not detected from the v₃ level. These results are discussed in terms of SSH type theoretical calculations, and comparison is made with the results obtained for other members of the methyl halide series, namely CH₃F, CH₃Cl and CH₃Br.     

Laser raman spectra of the stable low-temperature phase of ferrocene

Laser Raman spectra of ferrocene crystal are recorded for the stable (orthorhombic) and metastable (triclinic) low-temperature phases, and the stable and undercooled (monoclinic) high-temperature phases.The skeletal vibrational modes [v₄(A_1g) and v₁₆(E_1g)], the CH bending (⊥e) mode [v₂₅(E_2g)], and the lattice modes below 100 cm^?1 show characteristic changes among these phases.     

Infrared and Raman spectra of tripotassium dihydrogen triphosphate and its ammonium derivatives

In order to obtain information on the completeness of potassium dihydrogen triphosphate topochemical ammonization the authors have studied the i.r. and Raman spectra of K₃H₂P₃O₁₀·H₂O, products of its interaction with gaseous ammonia and ammonium—potassium triphosphate (K:NH₄ = 3:2) precipitated from aqueous solution. The assignments of the absorption bands (2000-400 cm⁻¹; 293 and 100 K) have been made. The spectra of double salts obtained by different methods, in contrast to their X-ray diffraction patterns, have been found to be identical. This is indicative of the completeness and partial topotaxity of acidic salt topochemical ammonization. The ammonization process can be investigated through the changes in intensity of the bands pertaining to the vibrations of the -PO₃H end group: v_sPO^*₂, vPO(H) and δPO(H).     

Unexpected frequency shifts and linewidth changes for rovibrational lines in the infrared emission spectra of CO2 excited by active nitrogen

Fourier transform emission spectra from flowing CO₂ excited by active nitrogen have been recorded in the 4.5 μm region, with a resolution of 0.0054 cm⁻¹, for different time intervals between the mixing of the two gases and observation of the emission. Significant frequency shifts (reaching 30 times the absolute uncertainty of the experimental frequencies) and linewidth changes are observed depending on the time interval and the value of the quantum number v₃, for thousands of rovibrational lines belonging to v₁v¹₂v₃ → v₁v¹₂(v₃-1) vibrational transitions.     

Volumetric, viscometric and refractive index behavior of some α-amino acids in aqueous tetrapropylammonium bromide at different temperatures

Densities, ρ, viscosities, η, and refractive indices, n _D, of glycine (Gly), DL-alanine (Ala), DL-valine (Val) (0.05, 0.10, 0.15, 0.20, 0.25 mol kg^?1), and L-leucine (Leu) (0.02, 0.05, 0.10 mol kg^?1) in water and in 0.20 mol kg^?1 aqueous tetrapropylammonium bromide (TPAB) have been measured at 298.15, 303.15, 308.15, and 313.15 K. The density data have been utilized to calculate apparent molar volumes, ?_v, partial molar volumes at infinite dilution, ?_v°, and partial molar volumes of transfer, ? _v°(tr) of amino acids. The viscosity data have been analyzed by means of Jones-Dole equation to obtain Falkenhagen coefficient, A, and Jones-Dole coefficient, B, free energy of activation of viscous flow per mole of solvent, Δµ₁°*, and solute, Δµ₂°*, and enthalpy, ΔH*, and entropy of activation, ΔS*, of viscous flow. The refractive index data have been used to calculate molar refractivity, R _D, of amino acids in aqueous tetrapropylammonium bromide solutions. It has been observed that ?_v°, B-coefficient and Δµ₂°* vary linearly with increasing number of carbon atoms in the alkyl chain of amino acids, and they were split to get contributions from the zwitterionic end groups (NH₃ ⁺, COO^-) and methylene group (CH₂) of the amino acids. The behavior of these parameters has been used to investigate the solute-solute and solute-solvent interactions as well as the effect of tetrapropylammonium cation (C₃H₇)₄N⁺ on these interactions.     

Vibrational energy exchange between CO(v=1) and 14N2 and CO(v=1) and 15N2XXXured to 60 k in the gas phase

Laser fluorescence technique has been used to measure (VV) exchange rates between CO(v = 1) and ¹⁴N₂ and ¹⁵N₂ XXX At 65 K exchange to ₁₅N₂ has 65 times the higher rate constant. Comparison with data for (VV) exchange in liquid ₂ shows that the isolated binary collision theory does not hold for the case of CO(v = 1) and ¹⁴N₂.     

Single-crystal raman study of dirhenium decacarbonyl

A single-crystal Raman study of Re₂(CO)₁₀ is reported from which 20 of the 21 Raman-active modes of this D_4d molecule have been assigned. All six lattice modes were identified below 70 cm^-1. In respect of the long-disputed assignment of v (Re--Re), for which two possibilities exist (107 and 129 dm^-1), the balance of the new evidence is in favour of the lower band. Comparisons are drawn with assignments for Mn₂(CO)₁₀ and Re(CO)₅X, (X = halogen), respectively and anomalies noted.     

Energy dependence of rotational and vibrational distributions of N2(C) for the Ar*(3P0,2) + N2(X) excitation transfer reaction

The Ar* + N₂(X) → N₂(C, v′, N′) + Ar excitation transfer reaction has been investigated experimentally in two different atomic beam experiments. The inelastic cross sections Q_{v′ = 0}(E) and Q_{v′ = 1}(E) to the v′ vibrational level have been measured in the energy range 0.06 ⩽ E(eV) ⩽ 6, using a crossed beam machine. Both cross sections show a behaviour typical for a curve crossing mechanism, with maximum values Q₀ = 8.0 Ų and Q₁ = 1.2 Ų at E = 0.16 eV and E = 0.13 eV, respectively. The oscillatory behaviour of the ratio Q₁(E)/Q₀(E), as first observed by Cutshall and Muschlitz, is also present in our data. Within the model of Gislason et al. the results indicate a decreasing bond stretching with increasing energy. As an alternative we discuss the possibility that the oscillation is due to a different energy dependence of the cross sections for the Ar*(³P₀) and Ar*(³P₂) fine structure states in the mixed beam of metastable Ar*. The vibrational and rotational distributions have also been measured at E = 0.065 eV in a small scale atomic beam-scattering cell experiment, which can be considered as an intermediate between a bulk experiment and a crossed beam experiment. The relative vibrational populations are n_v′ = 100, 16.0, 3.03 and 0.31 for v′ = 0 through 3, with rotational “temperatures” of T_rot,v′ = 1960, 1010, 370 and 130 K. Pronounced deviations (“hump”) of the Boltzmann rotational distributions occur at N′ ≈ 27 for v′ = 0, 1 and 2, with a fractional population of 1, 3 and 11%. For v′ = 0 the “hump” is largely obscured by overlap with the v′ = 1 bandhead. These bimodal distributions are in qualitative agreement with the results of Nguyen and Sadeghi for v′ = 0. The results are discussed within the framework of a curve crossing mechanism with the Ar⁺-N⁻₂ diabatic potential as an intermediate. By assuming equal charges on both N atoms the Coulomb potential of the collinear orientation lies lower (0.45 eV at R = 2.5 Å) than the perpendicular orientation, with the consequence of different transfer probabilities for both orientations. Within a classical model or rotational excitation the final N′ values can be calculated for both orientations, resulting in much higher N′ values for the perpendicular orientation. This mechanism supplies a qualitative explanation for the observed bimodal rotational distributions.     

Velocity modulation laser spectroscopy of vibrationally excited CF+ determination of the molecular potential function

The lowest six vibrational hot bands of CF⁺ have been measured in a helium/C₂F₆ discharge by velocity modulation laser spectroscopy. A total of 56 transitions has been fitted to Dunham expansion for v = 0–7, yielding the parameters: ω_e = 1792.6654(18) cm⁻¹B_e = 1.7204176(75) cm⁻¹, Y₂₀, = −13.22968(54) cm⁻¹, and D₀ = 62086(30) cm⁻¹. The rotational temperature of CF⁺ in the plasma is near 650 K and the vibrational temperature is approximately 5200 K.     

Vibrational energy transfer between 12C16O and 13C16O

The rate of the energy exchange process ¹²C¹⁶O (v= 1)+ ¹³C¹⁶O (v= 0) ? ¹²C¹⁶O (v= 0) +¹³C¹⁶O (v= 1) + 47.2 cm^?1 has been measured by laser-induced fluorescence, k₂ = (7.2 ± 0.3) × 10⁴ s^?1 Torr^?1 at 293 K. This result is in reasonable agreement with that predicted by theories based on long-range dipole-dipole interactions     

Vibrational relaxations of NO by atomic oxygen

A laser-induced fluorescence method has been used to study the vibrational relaxation of NO by atomic oxygen, i.e. NO(v=1) + O — NO(v=0) + O(2). The NO was excited indirectly by vibrational-vibrational energy transfer from HCI(v=1), these molecules having been prepared using the output from a pulsed HCl chemical laser. The experiments yield: k₂=(6.5 ± 0.7) × 10^?11 cm³ molecule^?1 s^?1 at (296 ± 3) K.