Vibrational overtone spectroscopy of saturated hydrocarbons dissolved in liquefied Ar, Kr, Xe, and N2

This article presents a collection of vibrational overtone spectra of hydrocarbons in cryogenic solutions. Vibrational overtone spectra of ethane and propane dissolved in liquid argon and n-butane and isobutane dissolved in liquid krypton were recorded between 5000 and 14,000 cm(-1). Spectral regions for the first four overtones were measured using a Fourier transform spectrophotometer. The fifth overtone (Deltaupsilon = 6) spectra were recorded with a double beam (pump-probe) thermal lens technique using concentrations as low as 10-3 mole fraction. We obtained the C-H (Deltaupsilon = 6) spectra of (a) liquid ethane at 100 K and ethane in solutions in liquid Ar at 92 K and liquid N2 at 85 K, (b) liquid propane at 148 K and propane in liquid Ar at 93 K, (c) n-butane in liquid Kr at 129 K, (d) n-pentane in liquid Xe at 160 K, and (e) isobutane liquid at 135 K and isobutane in liquid Kr at 130 K. Local-mode parameters were calculated for primary, secondary, and tertiary C-H oscillators in solution and compared with gas-phase local-mode parameters. The peak frequency shift (Deltaomega) from gas phase to solution is explained by the change in harmonic frequency and anharmonicity in solution with respect to the gas-phase values. The bandwidth (Deltaomega1/2) of the (Deltaupsilon = 6) C-H absorption bands of ethane in solution can be explained in terms of collisions with the solvent molecules.     

Scattering of low energy He2+ ions by Ne,Ar, and Kr atoms

Experimental studies of collisions of He²⁺ ions with Ne, Ar, and Kr atoms have been carried out at laboratory kinetic energies in the range 8 ? E₁ ? 10 eV. For each collision pair, relative differential cross sections for elastic scattering, and for the formation of He⁺ by single charge transfer [e.g., He²⁺ + R = He⁺ + (R⁺)^*] were measured. Information concerning the initial states of the charge transfer products was also obtained, from measurements of the kinetic energy distributions of the He⁺ + He = Ne⁺(2s 2p⁶²S) ± He⁺(²S), whereas for the other systems, transfer proceeds via a number of channels. The He⁺-ion kinetic energy measurements indicated that for He²⁺. Ar both Ar⁺ both Ar⁺ and Ar²⁺ are formed in transfer, and that for He²⁺, Kr only Kr²⁺ (and no Kr⁺) was formed.The differential elastic scattering patterns were analyzed by means of cross section calculations based on an approximate form of the optical model. These calculations indicated that the pronounced shoulders observed in the σ_el(θ) versus θ curves arose from scattering from an attractive potential well, in the presence of concurrent inelastic scattering. Using parametrized Morse potentials to represent the ground electronic states of (HeNe)²⁺, (HeAr)²⁺, and (HeKr)²⁺, the corresponding well-depth are estimated to be, respectively: 1.0 eV, 2.1 eV and 2.6 eV.     

Observation of inner-shell triplet states of CO2 and N2O and of inner-shell fine structure in Kr and Xe

Inner-shell singlet-triplet transitions in CO₂ and N₂O have been observed by the electron energy-loss technique at low values of the incident electron energy, typically 1.4 times the excitation energies of the states. The same technique has been used to observe fine structure in transitions near the M_4.5 edges in Kr and the N_4.5 edges in Xe.     

Field-assisted photodesorption of He,Ne, Ar,Kr and CO ions from W

The electric field dependence of the photodesorption yield of several noble gases from a tungsten surface was studied. Above a threshold field the desorption rate of ions increased until the field reached a characteristic value, which corresponds closely to the “best image field” observed for the respective gas in field ion microscopy. At still higher fields, the rate of photodesorption decreased rapidly. The intensity of the desorption signal increased in the order Kr ⪡ Ar < Ne ≈ He. Much less influence of field strength was found with a strongly chemisorbed species, CO.     

Evaporatively cooled M+ (H2O)Ar cluster ions: infrared spectroscopy and internal energy simulations

Rotationally resolved IR spectra of M+ (H2O)Ar cluster ions for M=Na, K, and Cs in the O-H stretch region were measured in a triple-quadrupole mass spectrometer. Analysis of the spectra yields O-H stretch vibrational band origins and relative IR intensities of the symmetric and asymmetric modes. The effect of the alkali-metal ions on these modes results in frequency shifts and intensity changes from the gas phase values of water. The A-rotational constants are also obtained from the rotational structure and are discussed. Experimentally, the temperatures of these species were deduced from the relative populations of the K-rotational states. The internal energies and temperatures of the cluster ions for Na and K were simulated using RRKM calculations and the evaporative ensemble formalism. With binding energies and vibrational frequencies obtained from ab initio calculations, the average predicted temperatures are qualitatively consistent with the experimental values and demonstrate the additional cooling resulting from argon evaporation.     

Method/basis set dependence of the traceless quadrupole moment calculation for N2, CO2, SO2, HCl,CO, NH3, PH3, HF,and H2O

Dipole moments and traceless quadrupole moments for a training set of nine molecules—N₂, CO₂, SO₂, HCl, CO, NH₃, PH₃, HF, and H₂O—were deduced from the final optimized density matrices of a series of ab initio calculations, thereby employing different levels of theory with varying basis set quality. All the results were obtained in a true ab initio sense, meaning that at a certain combination of method/basis set, the configurations of the molecules were first subjected to a geometry optimization and only afterwards the dipole and traceless quadrupole moments were derived for the final relaxed structures. All results could be compared to experimental data, thus the quality of the different models with respect to applicability and reliability of calculating molecular moments without any knowledge of structural details of the equilibrium geometries could be evaluated. Generally, a combination of methods that take into account correlation effects, together with a high‐level basis set, was found to yield molecular moments close to the experimental values. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Photofragmentation of cluster ions: the visible photoabsorption spectrum of Ar2N 2 +

The absolute cross section for photodissociation of Ar₂N ₂ ⁺ was measured as a function of wavelength in the 470–550 nm range. A structureless broad band was observed; the cross section has a maximum of ～ 210 × 10^?18 cm² at ～ 500 nm. The measurement of the photofragment time-of-flight spectrum shows that(1) N ₂ ⁺ , Ar⁺ and Ar ₂ ⁺ are produced in the photodissociation of Ar₂N ₂ ⁺ in the wavelength range studied, and that(2) the observed visible absorption band is ascribable to a parallel-type transition of Ar₂N ₂ ⁺ , which possibly retains a linear geometry.     

Experimental measurement of the mobilities of atomic and dimer Ar, Kr, and Xe ions in their parent gases

A new experimental technique for measuring the mobilities of positive ions in their parent gases is presented. The technique was applied to the rare gases, Ar, Kr, and Xe, and, for pressures typically below 10 Torr, two different types of positive ions were observed. The reduced mobilities of these ions in their parent gases were measured as a function of E/N, the ratio of the electric field strength to the gas number density, at a temperature of 300±1 K. The results were compared with others available in the literature and the two ions were identified as being the atomic and the dimer rare gas ions. The results are in good agreement with those from other authors. Space charge and impurities effects are discussed.     

A kinetic study of the reactions of Ca+ ions with O3, O2, N2, CO2 and H2O

The reactions between Ca(+)(4(2)S(1/2)) and O(3), O(2), N(2), CO(2) and H(2)O were studied using two techniques: the pulsed laser photo-dissociation at 193 nm of an organo-calcium vapour, followed by time-resolved laser-induced fluorescence spectroscopy of Ca(+) at 393.37 nm (Ca(+)(4(2)P(3/2)-4(2)S(1/2))); and the pulsed laser ablation at 532 nm of a calcite target in a fast flow tube, followed by mass spectrometric detection of Ca(+). The rate coefficient for the reaction with O(3) is essentially independent of temperature, k(189-312 K) = (3.9 +/- 1.2) x 10(-10) cm(3) molecule(-1) s(-1), and is about 35% of the Langevin capture frequency. One reason for this is that there is a lack of correlation between the reactant and product potential energy surfaces for near coplanar collisions. The recombination reactions of Ca(+) with O(2), CO(2) and H(2)O were found to be in the fall-off region over the experimental pressure range (1-80 Torr). The data were fitted by RRKM theory combined with quantum calculations on CaO(2)(+), Ca(+).CO(2) and Ca(+).H(2)O, yielding the following results with He as third body when extrapolated from 10(-3)-10(3) Torr and a temperature range of 100-1500 K. For Ca(+) + O(2): log(10)(k(rec,0)/cm(6) molecule(-2) s(-1)) = -26.16 - 1.113log(10)T- 0.056log(10)(2)T, k(rec,infinity) = 1.4 x 10(-10) cm(3) molecule(-1) s(-1), F(c) = 0.56. For Ca(+) + CO(2): log(10)(k(rec,0)/ cm(6) molecule(-2) s(-1)) = -27.94 + 2.204log(10)T- 1.124log(10)(2)T, k(rec,infinity) = 3.5 x 10(-11) cm(3) molecule(-1) s(-1), F(c) = 0.60. For Ca(+) + H(2)O: log(10)(k(rec,0)/ cm(6) molecule(-2) s(-1)) = -23.88 - 1.823log(10)T- 0.063log(10)(2)T, k(rec,infinity) = 7.3 x 10(-11)exp(830 J mol(-1)/RT) cm(3) molecule(-1) s(-1), F(c) = 0.50 (F(c) is the broadening factor). A classical trajectory analysis of the Ca(+) + CO(2) reaction is then used to investigate the small high pressure limiting rate coefficient, which is significantly below the Langevin capture frequency. Finally, the implications of these results for calcium chemistry in the mesosphere are discussed.     

Proton transfer reactions from H3+ ions to N2, O2, and CO molecules

The rate constants for proton transfer from H₃⁺ ions to N₂, O₂, and CO have been measured as function of hydrogen buffer gas partial pressure. The rate constant for proton transfer from H₃⁺ to N₂ shows a very large pressure dependence, increasing from 1.0 × 10^?9 cm³/s at low H₂ partial pressures to 1.7 × 10^?9 cm³/s at high H₂ partial pressures. The rate constants for proton transfer from H₃⁺ to O₂ and CO are constant with partial pressure of H₂; giving values of 6.4 × 10^?10 cm³/s and 1.7 × 10^?9 cm³/s, respectively. The roles of excess vibrational energy in H₃⁺ ions and of equilibrium between forward and back reaction are discussed. Back reaction is observed only for the reaction of H₃⁺ ions with O₂, and an equilibrium constant of K = 2.0 ± 0.4 at 298 K has been determined. From these data the proton affinity of O₂ is deduced to be 0.47 ± 0.11 kcal/mole higher than that of H₂.     

Appearance of interatomic Coulombic decay in Ar, Kr, and Xe homonuclear dimers

Interatomic Coulombic decay (ICD) is observed in the rare gas homonuclear dimers Ar2, Kr2, and Xe2 with photoion spectroscopy techniques. Inner valence ionization of the outer ns shell of these systems is known to create a metastable state that dissociates to form a ground state ion and a neutral excited fragment. Inner valence ionization to form ns satellite states leads to similar dissociations, but the neutral fragment gets all the more excited as the internal energy of the ns satellite state increases. When enough excitation energy is transferred to reach the ionization potential, ICD occurs. ICD threshold is observed to coincide with the position of the A+A+ ground state in the Franck-Condon region.     

Correction of mass spectrometric isotope ratio measurements for isobaric isotopologues of O2, CO,CO2, N2O and SO2

Gas isotope ratio mass spectrometers usually measure ion current ratios of molecules, not atoms. Often several isotopologues contribute to an ion current at a particular mass‐to‐charge ratio (m/z). Therefore, corrections have to be applied to derive the desired isotope ratios. These corrections are usually formulated in terms of isotope ratios (R), but this does not reflect the practice of measuring the ion current ratios of the sample relative to those of a reference material. Correspondingly, the relative ion current ratio differences (expressed as δ values) are first converted into isotopologue ratios, then into isotope ratios and finally back into elemental δ values. Here, we present a reformulation of this data reduction procedure entirely in terms of δ values and the ‘absolute’ isotope ratios of the reference material. This also shows that not the absolute isotope ratios of the reference material themselves, but only product and ratio combinations of them, are required for the data reduction. These combinations can be and, for carbon and oxygen have been, measured by conventional isotope ratio mass spectrometers. The frequently implied use of absolute isotope ratios measured by specially calibrated instruments is actually unnecessary. Following related work on CO₂, we here derive data reduction equations for the species O₂, CO, N₂O and SO₂. We also suggest experiments to measure the required absolute ratio combinations for N₂O, SO₂ and O₂. As a prelude, we summarise historic and recent measurements of absolute isotope ratios in international isotope reference materials. Copyright © 2008 John Wiley & Sons, Ltd.     

Ionization gauge sensitivities of N2, O2, N2O,NO, NO2, NH3, CClF3 and CH3OH

A Bayard-Alpert (BA) gauge was used to determine apparent relative sensitivites S_rel,X for O₂, N₂O, NO, NO₂, NH₃, CClF₃ and CH₃OH from gauge calibration measurements in the range 1.3×10^?1 Pa≤p≤1.3·10^?3Pa. Nitrogen was used as a calibration standard.     

Modelling light diatomics trapped in rare gas matrices: H2, HD and D2 in Ar,Kr and Xe

The different models allowing the calculations of the rovibrational frequency shifts with respect to the free molecule of a molecular impurity embedded in a rare gas crystal are reviewed. It is shown that models which account for the translational motion of the impurity yield reliable results, the effects of the rare-gas translation seem to be less important. The different models currently used are described in detail and the computational procedures are discussed. Finally, it is shown that for heteronuclear diatomics, the translation-rotation coupling could play an important role.     

Kristallstruktur von Trisilber(I)amidosulfat-3-Ammoniak-2-Wasser,Ag3SO3N · 3NH3 · 2H2O

An X-ray crystal structure analysis of colourless Ag₃SO₃N · 3NH₃ · 2H₂O was carried out at room temperature:M=504.79, orthorhombic, P2₁2₁2₁,a=6.275 (1) Å,b=11.826 (2) Å,c=14.299 (12) Å,V=1061.10 ų,Z=4,d _x=3.160 Mgm^–3,F(000)=940, Mo K, =0.71069 Å (graphite monochromator), =5.60 mm^–1,R=4.71%,R _w=4.96% (982 reflections, 120 parameters). The structure consists of Ag ribbons; each Ag atom is linearly co-ordinated to two N atoms with distances corresponding to covalent Ag-N bonds; no Ag-O coordination is observed; the N atom of the SO₃N group is surrounded by three Ag atoms; compared to amidosulfuric acid, the SO₃N group shows significant deformation.

     

Theoretical study of Pt-Ng and Ng-Pt-Ng (Ng=Ar,Kr,Xe)

We have investigated the binding of noble-gas (Ng) atoms (Ng=Ar,Kr,Xe) with Pt atom by the ab initio coupled-cluster CCSD(T) method, taking into account the relativistic effects. It is shown that two Ng atoms can bind with Pt atom in linear geometry in the singlet lowest state where the second Ng atom attaches to Pt with the larger binding energy than the first Ng atom. The binding energy is evaluated as 8.2, 17.9, and 33.4 kcal/mol for Ar-Pt-Ar, Kr-Pt-Kr, and Xe-Pt-Xe, respectively, relative to the triplet ground state of the dissociation limit Pt ((3)D)+2Ng. The present results indicate that these Ng-Pt-Ng compounds are possible new gas-phase or matrix species.     

Threshold photoelectrons coincidence spectroscopy of the rare gases Ne,Ar, Kr and Xe

Threshold single photon double ionisation of the rare gases neon, argon, krypton and xenon has been studied in an electron-electron coincidence experiment. A new technique has been used where only near-zero energy electrons are detected and these are measured in coincidence. The spectrometer used here employs the penetrating field technique which provides very high detection efficiency, sensitivity and energy resolution. Relative partial double ionisation cross sections have been measured at threshold for then p⁴(³P,¹D and¹S) states of Ne⁺⁺, Ar⁺⁺, Kr⁺⁺ and Xe⁺⁺ and then sn p⁵ (³P and¹P) states of Ne⁺⁺, Ar⁺⁺ and Kr⁺⁺. The observed relative cross sections are in general agreement with a propensity rule for excitation of these states, except for the case of neon.     

Infrared spectra of monomeric thioformaldehyde in Ar,N2 and Xe matrices

Pyrolysis products of 1,3-dithietane were trapped in low-temperature matrices and their infrared spectra were recorded. The vibrational bands of monomeric H₂CS, which was not perturbed by other decomposition products, were identified in Ar, N₂ and Xe matrices. These results will be useful to evaluate the frequency shifts of H₂CS induced by the interaction with other molecules.