Evaluation of jet-cooled laser spectroscopy for simplifying infrared spectra

The effect of jet cooling on the vibration-rotation spectra of several polyatomic molecules has been investigated using diode-laser absorption spectroscopy. Vibration-rotation spectra in jet expansions is considered in terms of several factors including rotational and vibrational distributions, line strengths and the rotational structure of individual bands. The diode-laser spectra of PF₃, CF₃Cl, C₃H₆, C₂H₃F, and CH₃CCH recorded in a molecular beam are examined with the above criteria.     

Forbidden rotational spectra of axially symmetric polar molecules

In this paper we consider the rotational transitions induced by centrifugal distortion in polar or quasipolar symmetric top molecules belonging to the point groups C_n and C_nv (n ≥ 3). It is shown that in this series only the molecules of point groups C₃, C_3v, C₄, and C_4v may possess rotational spectra induced by first-order centrifugal distortion. A general expression is given for the effective dipole moment operator and for its matrix elements. The peak absorption coefficients for some of the strongest ΔK = 3 transitions of the CH₃D molecule have been calculated and compared with the peak absorption coefficients of allowed transitions.     

Equilibrium composition and the effective adiabatic exponent of a clustering carbon plasma

The equilibrium composition and the effective adiabatic exponent of a low-temperature carbon plasma containing eight components (C, C₂, C₃, C₄, C₅, C⁺, C₂⁺, and e) are calculated. The temperature and pressure ranges are found in which polyatomic clusters form in a gas flow. It is shown that the effective adiabatic exponent of the carbon plasma is a nonmonotonic function of temperature. In the parameter range where the plasma consists largely of polyatomic clusters, the adiabatic exponent is close to unity. It is noted that anomalously low values of the effective adiabatic exponent indicate a considerable concentration of polyatomic molecules in the plasma jet. Such values can be observed in experiments with a low-temperature carbon plasma flowing about bodies.     

Near infrared spectroscopy of organic acids: comparing OH and CH oscillator frequencies and intensities

This work investigates the vibrational spectroscopy of a series of organic acids, CH₃(CH₂)_nCOOH (n = 1-5), previously unobserved in the IR and near-IR (2000-15 000 cm⁻¹). The work obtains frequencies and relative intensities for all OH and CH stretching transitions. Comparison of the frequencies and intensities of CH and OH stretching transitions reveal interesting trends in acid chain length that are discussed. Literature values for acetic acid (CH₃COOH) and formic acid (HCOOH) are used to gain a broader understanding for the spectroscopy of the organic acids CH₃(CH₂)_nCOOH. The observation of several combination bands involving the CH and OH stretching vibrations and possible rotational isomer and hot band transitions are reported.     

Analysis of the CH3D Nonad from 2000 to 3300 cm

As part of the simultaneous analysis of line positions and intensities of the first two polyads of monodeuterated methane, the results achieved for the region 3-5 μm are reported. It involves the three highest fundamentals, (ν₁, ν₂, ν₄), overlapped by overtone (2ν₃, 2ν₅, 2ν₆) and combination (ν₃+ν₆, ν₃+ν₅, ν₅+ν₆) bands. The theoretical model was based on the global tensorial model implemented in the MIRS package. Some 10 000 line positions and 2400 line intensities have been modeled to ±0.000 88 cm⁻¹ and ±3.6% respectively, using measurements obtained at 0.0056 and 0.011 cm⁻¹ resolution with the Fourier transform spectrometer at National Solar Observatory located at Kitt Peak. The strongest band in this polyad is ν₄(E) at 3016.7 cm⁻¹ with a strength of 6.3×10⁻¹⁸ cm⁻¹/(molecule cm⁻²) at 296 K; the weakest band is 2ν₃(E) at 2597.7 cm⁻¹ with a strength of 1.9×10⁻²⁰ cm⁻¹/(molecule cm⁻²) at 296 K. The total calculated absorption arising from the CH₃D nonad is 8.95×10⁻¹⁸ cm⁻¹/(molecule cm⁻²) at 296 K.     

Site-blocking effects of preadsorbed H on Pt(1 1 1) probed by 1,3-butadiene adsorption and reaction

The influence of hydrogen coadsorption on hydrocarbon chemistry on transition metal surfaces is a key aspect to an improved understanding of catalytic selective hydrogenation. We have investigated the effects of H preadsorption on adsorption and reaction of 1,3-butadiene (H₂CCHCHCH₂, C₄H₆) on Pt(1 1 1) surfaces by using temperature-programmed desorption (TPD) and Auger electron spectroscopy (AES). Preadsorbed hydrogen adatoms decrease the amount of 1,3-butadiene chemisorbed on the surface and chemisorption is completely blocked by the hydrogen monolayer (saturation) coverage (θ_H = 0.92 ML). No hydrogenation products of reactions between coadsorbed H adatoms and 1,3-butadiene were observed to desorb in TPD experiments over the range of θ_H investigated (θ_H = 0.6-0.9 ML). This is in strong contrast to the copious evolution of ethane (CH₃CH₃, C₂H₆) from coadsorbed hydrogen and ethylene (CH₂CH₂, C₂H₄) on Pt(1 1 1). Hydrogen adatoms effectively (in a 1:1 stoichiometry) remove sites from interaction with chemisorbed 1,3-butadiene, but do not affect adjacent sites. The adsorption energy of coadsorbed 1,3-butadiene is not affected by the presence of hydrogen on Pt(1 1 1). The chemisorbed 1,3-butadiene on hydrogen preadsorbed Pt(1 1 1) completely dehydrogenates to H₂ and surface carbon upon heating without any molecular desorption detected, which is identical to that observed on clean Pt(1 1 1). In addition to revealing aspects of site blocking that should have broad implications for hydrogen coadsorption with hydrocarbon molecules on transition metal surfaces in general, these results also provide additional basic information on the surface science of selective catalytic hydrogenation of butadiene in butadiene-butene mixtures.     

The 2003 edition of the GEISA/IASI spectroscopic database

The content of the current (2003) version, GEISA/IASI-03, of the computer-accessible spectroscopic database, GEISA/IASI, is described. This “system” or database is comprised of three independent spectroscopic archives, which are (a) a database of individual spectral line parameters on 14 molecules, H₂O, CO₂, O₃, N₂O, CO, CH₄, O₂, NO, SO₂, NO₂, HNO₃, OCS, C₂H₂, N₂, and the related 51 isotopomers and isotopologues, representing 702,550 entries, in the spectral range 599-, (b) a database of spectral absorption cross-sections (6,572,329 entries related to six molecules, CFC-11, CFC-12, CFC-14, HCFC-22, N₂O₅, CCl₄), and a catalogue of microphysical and optical properties (mainly, the refractive indices) of atmospheric aerosols. The modifications and improvements, which have been implemented since the earlier editions of this database, in terms of content and management, have been explained in detail. GEISA/IASI has been created with the specific purpose of assessing the capability of measurement by the IASI instrument within the designated goals of ISSWG in the frame of the CNES/EUMETSAT European Polar System preparation.All the archived data can be handled through a user-friendly associated management software, which is posted on the ARA/LMD group web site at http://ara.lmd.polytechnique.fr.     

Total cross-sections for positron scattering by a series of molecules

The additivity rule is employed to obtain the total (elastic+inelastic) cross-sections for positron scattering from molecules including a number of diatomic, polyatomic molecules (H₂, N₂, HCl, CO₂, NH₃, SF₆, CH₄, C₂H₄ and C₃H₈) over an incident energy range of 10-1000 eV. The total cross-sections (TCS) of the constituent atoms of molecules are obtained by employing a complex optical model potential (composed of static, polarization and absorption potential). The present results are compared with experimental data and other theoretical calculations, good agreement is obtained in intermediate- and high-energy region. Received: 11 November 1997 / Revised: 23 March 1998 / Accepted: 16 June 1998     

Photoelectron spectroscopy of some thiocyanates,isocyanates and isothiocyanates

Photoelectron spectra of some thiocyanates (RSCN, R = CH₃, C₂H₅, n-C₄H₉), isocyanates (RNCO, R = C₂H₅, n-C₄H₉) and isothiocyanates (RNCS, R = C₂H₅, n-C₄H₉) have been measured, to study interactions between nonbonding and π orbitals, mainly localized on the SCN, NCO or NCS fragments. The spectral interpretation of CH₃SCN is based on semiempirical CNDO/S calculations, sum-rule considerations, and intensity differences between He(I) and HE(II) spectra. For the larger molecules, comparison of the spectra is used as an aid in the interpretation. In a number of aromatic isocyanates (o?, m?, p-tolylisocyanate and m?, p-chlorophenylisocyanate), interactions between the isocyanate group and the highest occupied π and σ orbitals of the phenyl ring are studied. Spectra are assigned on the basis of semiempirical INDO/S calculations.     

The pure rotational spectra of the lanthanum monohalides, LaF, LaCl, LaBr, LaI

Pure rotational spectra have been measured for all the major isotopomers of the lanthanum monohalides, LaF, LaCl, LaBr, and LaI, in their ground and (except for ) excited vibrational states. The spectra were observed with a cavity pulsed jet Fourier transform microwave spectrometer in the frequency range 5-24 GHz. The molecules were prepared by laser ablation of La metal and allowing the resulting plasma to react with SF₆, Cl₂, Br₂, or CH₃I precursor in an Ar carrier gas of the pulsed jet. For LaBr this is the first reported spectrum of any kind. Rotational constants, centrifugal distortion constants, nuclear quadrupole coupling constants, and nuclear spin-rotation constants have been determined for all the molecules. Accurate equilibrium (r_e) internuclear distances have given an indication of where the Born-Oppenheimer approximation is beginning to fail. From the centrifugal distortion constants and vibration-rotation (α_e) constants good estimates of the harmonic vibration frequencies and bond dissociation energies have been obtained. The halogen nuclear quadrupole coupling constants indicate the molecules to be highly ionic.     

Gas-phase Raman spectra of hot bands of fundamentals and combinations associated with the torsional vibration of s-trans-1,3-butadiene and its deuterated isotopologues

The gas-phase Raman spectra of 1,3-butadiene and its 2,3-d₂, 1,1,4,4-d₄, and d₆ isotopologues have been recorded with high sensitivity and resolution of 0.7 cm⁻¹. Hot band series of fundamentals and combinations involving the ν₁₃ torsional vibration of the s-trans rotamer have been observed for each of the isotopologues. Modes studied were ν₁₀ (CH wag), ν₁₂ (CH₂ twist), ν₁₀ + ν₁₂, ν₁₅ (CH₂ wag) + ν₁₆ (CH₂ twist), and ν₂₃ (CH₂ rock) + ν₂₄ (CCC deformation). The spacings of the quantum states of the torsional contribution were found to decrease with additional excitation of this mode (ν₁₃) in the upper vibrational states except for the ν₂₃ + ν₂₄ combination state.     

The vibrational levels of methane obtained from analyses of high-resolution spectra

Methane and its tetrahedral isotopologues are spherical-top molecules whose high-resolution rovibrational spectra can only be analyzed in detail, thanks to sophisticated symmetry-adapted tensorial models. However, the effective Hamiltonian parameters of such models do not give direct access to the positions of the vibrational sublevels. In this paper, we present a calculation of the vibrational level positions for ¹²CH₄, ¹³CH₄, ¹²CD₄ and ¹³CD₄ performed using the effective Hamiltonian parameters obtained through recent analyses. We also include the results of a re-analysis of the octad system of ¹²CH₄ performed with a higher order of the development which slightly improves the previous work on this polyad.     

A general local-mode theory for high energy polyatomic overtone spectra and application to dichloromethane

A new model is developed to describe the overtone spectra of polyatomic molecules containing XH_n moieties. The infrared absorption is described as corresponding to excitation of localized modes of vibration rather than a set of symmetry allowed combinations of anharmonic normal modes. The possibility of assigning new bands in the more complex regions of the overtone spectra which involve combinations of both stretching and bending modes is examined and illustrated using the overtone spectrum of ammonia. The overtone spectrum of dichloromethane is recorded in the range λ = 9260 Å to λ = 5300 Å, and the CH overtone bands at 8850 Å, 7223 Å, and 6165 Å corresponding to the Δv_CH = 4, 5, and 6 overtones are identified. Specific features of these bands are discussed in detail in relation to the model. The common features and simplicity of the Δv_CH = 4 overtone bands of a series of halomethanes and ethanes are also interpreted in terms of the model.     

An experimental and quantum-chemical study of the Raman spectra and rotational isomerism of thiophosphites (RS) n PCl3 − n (R = Me, Et; n = 1, 2)

The Raman spectra of different conformations of CH₃SPCl₂, C₂H₅SPCl₂, and (C₂H₅S)₂PCl are studied within the framework of the density functional theory (B3LYP/6-31G* and B3LYP/6-31+G*) using the method of scaling of force fields. Comparison of the calculated and experimental spectra makes it possible to interpret the latter and to establish the existence of trans and gauche conformers of these molecules, which are formed due to internal rotation about the P-S and S-C bonds. This comparison also shows that, for the prediction of the degrees of depolarization of Raman lines to be correct, it is necessary to introduce diffuse functions into the basis set.     

Configuration dependence of photon stimulated ion desorption from methyl ester compounds induced by core excitation

Photon stimulated ion desorption (PSID) from methyl ester terminated self-assembled monolayer (MHDA-SAM, HS(CH₂)₁₅COOCH₃) and methyl mercaptoacetate (MA, HSCH₂COOCH₃) on Ag has been investigated using soft X-ray in the C and O K-edge regions. In MHDA-SAM on Ag, site-selective ion desorption has been clearly observed at resonant core excitations of C_1s, O_1s(OCH₃) → σ^∗(OCH₃) and O_1s(OCH₃) → σ^∗(COCH₃). Ion intensity in MA on Ag is obviously reduced for (n = 1-3) at C_1s, O_1s(OCH₃) → σ^∗(OCH₃) excitations, and no site-selective reaction at O_1s(OCH₃) → σ^∗(COCH₃) excitations has been observed. These reactions may be influenced by configurational difference of reactive sites. It is suggested that surface effects on the selective reaction due to positioning methyl ester group near the surface plays an important role.     

Electron paramagnetic resonance of gamma irradiated [(CH3)4N]InCl4 and [(CH3)4N]2CdCl4 single crystals

Gamma irradiated [(CH₃)₄N]InCl₄ and [(CH₃)₄N]₂CdCl₄ single crystals were investigated by electron paramagnetic resonance at ambient temperature, and it has been found that both compounds indicate the existence of (CH₃)₃N⁺ radicals. The g factors were found to be isotropic, and the hyperfine constant for H atoms was measured as 2.86 mT and is isotropic for this radical in these substances. The hyperfine coupling constant of the N nucleus with the hole in (CH₃)₃N⁺ in [(CH₃)₄N]InCl₄ was found to be anisotropic with the A_zz=2.92, A_yy=1.62 and A_xx=1.40 mT. From these, it has been revealed that the C_3v-axis of (CH₃)₃N⁺ radical performs rotational or jumping reorientational motions around a fixed axis, in addition to the rotations of protons in CH₃ groups and the rotational motions of CH₃ groups around the C_3v-axis of the radical. The g, and the hyperfine coupling factors of the N nucleus were isotropic in (CH₃)₃N⁺ in [(CH₃)₄N]₂CdCl₄. This indicates the motional behaviour of the radical in this compound is as in a liquid. This isotropic behaviour of the hyperfine coupling constants was found to be same until the attainable lowest temperature of 113 K in our laboratory.     

Collision-induced rovibrational energy transfer in small polyatomic molecules: the role of intramolecular perturbations

ABSTRACT

Various forms of time-resolved optical double-resonance spectroscopy facilitate rotationally resolved measurements of collision-induced intramolecular vibration-to-vibration (V–V) energy-transfer processes, which take a gas-phase polyatomic molecule from one distinct rovibrational energy level to another. Of longstanding mechanistic interest are questions concerning the extent to which such V–V energy transfer (ET) may be influenced by intramolecular perturbations – notably Fermi resonance (and other anharmonic mixing effects) and Coriolis coupling – within polyatomic molecular rovibrational manifolds of interest. It is evident that quantum-mechanical interference effects can arise, either inhibiting or enhancing the probability of collision-induced ET in perturbed rovibrational manifolds of certain small gas-phase polyatomic molecules, notably CO₂, D₂CO and C₂H₂. This article focuses on a blend of high-resolution rovibrational spectroscopy (characterising initial and final molecular levels and their intramolecular perturbations) and collision dynamics (with colliding molecules defined in terms of isolated-molecule spectroscopic basis states). It aims to offer fresh insights and to consider some apparent mechanistic anomalies (e.g. collision-induced quasi-continuous background effects in the 4ν_CH rovibrational manifold of C₂H₂). Various reported experiments and related theoretical treatments are critically re-examined, in order to pose and address mechanistic questions some of which still challenge detailed understanding.     

Global fit of the high-resolution infrared spectrum of D2S

High-resolution Fourier-transform spectra of the D₂S molecule in the regions of polyads of interacting vibrational states v = 3/2, 2, 5/2, 3 and 7/2 (v = v₁ + v₂/2 + v₃) were recorded for the first time with a Bruker IFS 120 Fourier-transform interferometer and analysed. A global fit of all currently available rotation-vibration energies has been made for 22 vibrational states of the D₂S molecule. The resulting set of 231 parameters reproduces all the initial experimental data (about 3670 vibration-rotation energies which correspond to more than 9700 ro-vibrational transitions with J^max = 25) with accuracies close to the experimental uncertainties.     

Atomic level analysis of biomolecules by the scanning atom probe

Utilizing the unique features of the scanning atom probe (SAP) the binding states of the biomolecules, leucine and methionine, are investigated at atomic level. The molecules are mass analyzed by detecting a single atom and/or clustering atoms field evaporated from a specimen surface. Since the field evaporation is a static process, the evaporated clustering atoms are closely related with the binding between atoms forming the molecules. For example, many thiophene radicals are detected when polythiophene is mass analyzed by the SAP. In the present study the specimens are prepared by immersing a micro cotton ball of single walled carbon nanotubes (SWCNT) in the leucine or methionine solution. The mass spectra obtained by analyzing the cotton balls exhibit singly and doubly ionized carbon ions of SWCNT and the characteristic fragments of the molecules, CH₃, CHCH₃, C₄H₇, CHNH₂ and COOH for leucine and CH₃, SCH₃, C₂H₄, C₄H₇, CHNH₂ and COOH for methionine.