Potential Energy Curves for Cu65 Cl36

Experimental potential energy curves have been constructed for the molecule Cu⁶⁵ Cl³⁵ by the Rydberg-Klein-Rees-Vanderslice method. Perturbations in the B'πstate have been predicted due to the C'πstate and large interactions have been observed in the D'π state which have been discussed. The dissociation energy for the Cu⁶⁵ Cl³⁵ molecule has been estimated (2.5ev) by a relation derived from Lippincott three parameter potential function.     

The microwave spectrum,harmonic force field,and structure of difluorodichloromethane

Very large numbers of rotational transitions have been accurately measured for ¹²CF₂³⁵Cl₂, ¹²CF₂³⁵Cl³⁷Cl, and ¹³CF₂³⁵Cl₂, and have been analyzed for rotational constants and quartic centrifugal distortion constants. The distortion constants have been combined with vibrational wavenumbers (both from the literature and from the present work), and with ab initio force constants also evaluated in the present work, to give an approximate harmonic force field. The rotational constants and force field have been used to evaluate ground state effective, substitution, and ground state average structures for the molecule.     

Theoretical study of the photoelectron spectra of gaseous Cu3Cl3

Ab initio calculations have been performed to interpret the photoelectron spectrum of gaseous cuprous chloride, Cu₃Cl³. Density functional calculations revealed Cu₃Cl₃ to be a planar cyclic D_3h molecule. Koopmans' theorem and two-hole/one-particle calculations with canonical Hartree-Fock orbitals were used to interpret the vertical ionization energies. These were compared with similar calculations using B3LYP Kohn-Sham orbitals. The results confirm the claim by Casida that Kohn-Sham orbitals mimic Dyson orbitals.     

Diode-laser radiation absorption of CF2Cl2 around 921 cm−1 in a supersonic jet

With a diode laser we have studied the spectral region around 921 cm^–1 of the CF₂Cl₂ molecule cooled in a free jet. Accurate studies of the intensity of two vibrorotational bands have enabled us to determine their assignment. In addition, the rotational structure has been partially resolved, and approximate fitting parameters have been deduced. The simultaneous use of a diode laser and a free jet has proved to be useful in correctly identifying the origin of the absorption bands.     

On the delay mechanism of Cl<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> diatomic anion dissociation up to the microsecond timescale

The dissociative capture of slow electrons by tetrachlorethylene (C₂Cl₄) has been investigated by resonant electron capture negative ion mass spectrometry. Metastable ions with fractional mass numbers 7.5, 17.5, and 19 corresponding to the C₂Cl₄⁻ → Cl⁻ + C₂Cl₃ and Cl₂⁻ → Cl⁻ + Cl decays occurring at the microsecond timescale have been detected. It has been revealed that Cl₂⁻ anions, which are fragment ions, can dissociate at the microsecond timescale, which is very surprising for a system with one internal degree of freedom. This process is assumingly attributed to the rotational excitation of Cl₂⁻ anions. Thus, the experimental estimate of the time of rovibronic relaxation in the Cl₂⁻ anion has been obtained.     

DFT study of the water/MgO(1 0 0) interface in acidic and basic media

Periodic-DFT has been used to study the acid-base properties of MgO(1 0 0) layers interconnected with an ice filling. The insertion of HCl by substitution of one water molecule shows that all the protons are adsorbed on the surface oxygen atoms forming hydroxyl groups; the Cl⁻ ions are weakly bound to surface cations, generating a monolayer with the adsorbed water molecules. For the insertion of NaOH also by substitution of one water molecule, it is found that OH⁻ ions remain in solution close to the Na⁺ ions, forming ion pairs or chains. Depending on the number of water molecules present, the sodium ions are bi-, tri- or tetra-coordinated. Finally, some aspects concerning corrosion have been highlighted.     

Microscopic structure of liquid dimethyl sulphoxide and its electrolyte solutions: molecular dynamics simulations

Molecular dynamics (MD) simulations of pure dimethyl sulphoxide (DMSO) and solutions of Na⁺, Ca²⁺, Cl^?, NaCl and CaCl₂ in DMSO have been performed at 298.15 K and 398.15 K in NVT ensembles by using a four-interaction-site model of DMSO and reaction field method for Coulombic interactions. The structure of solvent, ion-solvation shells and ion-pairs have been analysed by employing a concept of coordination centres and characteristic vectors of the solvent molecule. Results are given for atom-atom (corresponding to DMSO), ion-atom and ion-ion radial distribution functions (RDFs), orientation of the DMSO molecules and their geometrical arrangements in the first solvation shells of the ions (Na⁺, Ca²⁺, Cl^?). A preferential formation of cyclic dimers with antiparallel alignment between dipole moments of nearest-neighbour molecules in the pure solvent is found. Geometrical models of the first coordination shells of the ions in ‘infinitely dilute solutions’ are proposed. Ion-ion RDFs in NaCl-DMSO and CaCl₂-DMSO solutions reveal the presence of both solvent separated (SSIP) and contact (CIP) ion pairs. The structures of the solvation shells of such ion pairs are also discussed.     

The millimeter wave spectrum of phosphorus oxychloride

Millimeter wave rotational spectra of phosphorus oxychloride (OPCl₃) in the ground and excited vibrational states have been recorded and analyzed. The v₅ = 1 and v₆ = 1 state spectra show large splittings due to l resonance and the effect of the 2, -1 term r_t. Coriolis constants have been obtained for the two lowest degenerate states. The spectra of the asymmetric top species OP³⁵Cl₂³⁷Cl have been analyzed and centrifugal distortion constants obtained. These have been used to determine the harmonic force field of the molecule.     

Pretransitional behaviour in nematic liquid crystals

A simple (four sites on the water molecule) potential for Cl^-/H₂O has been generated from six gradient calculations. The potential is in reasonable agreement with the extensive SCF calculations of Dacre.     

Submillimeter laser action of CW optically pumped CF2Cl2 (Fluorocarbon 12)

Eleven new CW far infrared (FIR) laser lines have been observed in the 600 m–1200 m range from the CF₂Cl₂ (Fluorocarbon 12) molecule optically pumped by a CO₂ laser. A 510^–4–10^–3 accuracy is achieved in the measurement of the FIR wavelengths.The frequency offset between the CO₂ pump center and the absorption line centers are measured using the transferred Lamb dip technique. Owing to a recent spectroscopic study of the CF₂ ³⁵Cl₂ molecule three lines may be assigned with great confidence as rotational transitions in thev ₆ vibrational band 923 cm^–1 of this main isotope.     

Optical properties and the crystal structure of anhydrous gadolinium-trichloride

The Raman and i.r. reflection spectra of GdCl₃ have been studied in order to estabish the optically active fundamental frequencies. Gd³⁺?Cl^?)-and (Cl^??Cl^?)-force constants in GdCl₃ and in LaCl₃ and PrCl₃ have been calculated on the basis of a simple rigid ion model. It is found that the apparently anomalous spectra of GdCl₃ may be a result of a stronger (Cl^??Cl^?)-coupling constant than in the hexagonal rare earth trichlorides with lower Z on the metal ion. This peculiar status of GdCl₃ is related to the change of crystal structure in the series of Rare-Earth trichlorides from a hexagonal (La-…Gd-) Cl₃ to an orthorhombic (TbCl₃ DyCl₃) structure. Some properties of the electronic spectra are also discussed in this context.     

The quadratic potential function and average structure of sulphur dichloride,SCl2, from its microwave spectrum

The microwave spectra of ³²S³⁵Cl₂ in the ground (000) and v₂ = 1 excited vibrational (010) states, and of ³²S³⁵Cl³⁷Cl in the (000) state, have been measured. Values of the quadratic potential constants have been determined from the centrifugal distortion constants and the variation of the inertial defect with vibrational state. A partial substitution structure has been evaluated. The potential function has been used to obtain average structures of ³²S³⁵Cl₂ in the (000) and (010) states. The frequencies of the three fundamental vibrations of ³²S³⁵Cl₂ have been predicted, and agree extremely well with observed values. A comparison is made of the bonding in SCl₂ and related molecules.     

Further study of the microwave spectrum of chlorine lsocyanate: The substitution structure and nuclear quadrupole coupling

The microwave spectra of three further isotopic species of chlorine isocyanate (³⁵Cl¹⁵N¹²C¹⁶O, ³⁷Cl¹⁵N¹²C¹⁶O, ³⁵Cl¹⁴N¹³C¹⁶O) have been measured. From them we have obtained rotational constants, centrifugal distortion constants, and nuclear quadrupole coupling constants. The data are combined with earlier data (1) to confirm the planarity of the molecule, and to give a full substitution structure as follows: $\text{r}\text{(ClN) = 1.705 ± 0.005}\text{A}\text{?}$; $\text{r}\text{(NC) = 1.226 ± 0.005}\text{A}\text{?}$; $\text{r}\text{(CO) = 1.162 ± 0.005}\text{A}\text{?}$; < (ClNC) = 118°50′ ± 30′; < (NCO) = 170°52′ ± 30′, with Cl and O trans. We have also calculated the chlorine and nitrogen quadrupole coupling constants using the SCF-MO-CNDO method, and have obtained good agreement with the measured values. Evidence for in-plane π-bonding at nitrogen has been obtained.     

Assignment of 13C Resonances in the Phencyclone-Norbornadiene Adduct Via 2D NMR. 13C Evidence for Hindered Rotation of Unsubstituted Bridgehead Phenyl Rings

¹³C NMR chemical shift assignments were obtained for the Diels-Alder adduct of phencyclone with norbornadiene in CD₂Cl₂ and in CDCl₃ solution. The ¹³C spectrum at 50.3 MHz, as well as the ¹H spectrum at 200.1 MHz, show evidence for hindered rotation of the two unsubstituted bridgehead phenyl rings of the adduct at ambient temperatures. In CD₂Cl₂ solution, all 19 of the unique ¹³C nuclei of this molecule give rise to individual ¹³C resonances. The ¹H assignments which were made earlier, together with one-bond and long-range 2D heteronuclear correlation experiments, allowed the assignment of all ¹³C chemical shifts in the molecule.     

Temperature variation of the Debye-Waller factors of metal and halide ions in CsCl and CsBr powders by X-ray diffraction. I. Debye-Waller factors of Cs+ and Cl− ions in CsCl from room temperature to 90°K

The temperature variation of the Debye-Waller factors of Cs⁺ and Cl⁻ ions in CsCl powder has been studied using X-ray powder diffraction. A continuous flow cryostat has been used to record the diffractograms and the integrated intensities of the Bragg peaks at different temperatures have been obtained. The integrated intensities of the odd and even reflections have been analysed following the structure of the CsCl compound and the Debye-Waller factors of the Cs⁺ and Cl⁻ ions have been estimated. The results have been verified by structure factor least squares refinement. Theoretical shell model lattice dynamical calculations have been done using a 7-parameter model in the harmonic approximation and the values compared with the present X-ray measurements.     

Transmission of 3471 a laser radiation through Cl2 and Cl2-inert-gas mixtures

Experimental results are presented on transmission and pulse-delays of the output from a frequency- doubled ruby laser through Cl₂ and Cl₂-inert-gas mixtures. The experimental findings are consistent with the idea that the observed results are determined by competition between a not-understood quantum-mechanical coherence effect and dephasing collisions. On this assumption, we deduce reasonable estimates for applicable cross sections in collisions of Cl₂ with Cl₂, He or Ar. Since the upper state of the absorbing molecule is unstable in times of the order of 10^-12 sec, the McCall-Hahn theory for self-induced transparency is not applicable to our system.     

Infrared spectrum and molecular force field of CF2Cl2

The infrared spectrum of CF₂Cl₂ has been measured under medium resolution in the range 1600-400 cm^?1. More than 100 bands including fundamental, overtone, combination, and “hot” bands of the three isotopic species CF₂³⁵Cl₂, CF₂³⁵Cl³⁷Cl, and CF₂³⁷Cl₂ have been identified. The band contour studies have enabled the fundamental vibrations to be unambiguously assigned, including the modes ν₃ and ν₇, the positions of which were previously in doubt. The observed values for CF₂³⁵Cl₂ in conjunction with the frequency shift data for CF₂³⁵Cl³⁷Cl and CF₂³⁷Cl₂ have been used in determining a general valence force field, which adequately describes the system investigated. A Fermi resonance interaction between ν₈ and ν₃ + ν₉ levels for the three isotopic species has been interpreted. The corresponding perturbations between those levels obtained by adding ν₂ or ν₅ to both ν₈ and ν₃ + ν₉ have also been found and the related features carefully investigated.     

Quenching and enhancing of SERS of methyl orange after the addition of chlorine and nitrate anions

The influence of Cl⁻ and NO₃⁻ anions on surface enhanced Raman scattering (SERS) of methyl orange adsorbed on “chemical pure” silver colloids was studied. It was found that NO₃⁻ could give rise to a large enhancement of SERS of methyl orange, while Cl⁻ could obviously weaken the SERS intensity of this molecule. Both quenching and enhancing effects were discussed and compared with each other. It indicated the coadsorbed process of these adsorbed species, and different adsorption behaviors of the molecules on silver surface directly resulted in the difference. In addition, the results of TEM pictures and UV-visible spectral experiments have also confirmed the conclusion above.     

High-Resolution Stimulated Raman Spectroscopy of Cl2, Cl2, and ClCl

A high-resolution rovibrational Raman spectrum of a sample of Cl₂ has been recorded at room temperature using a quasi-cw stimulated Raman technique. Three Q-branch structures belonging to the fundamental vibrations of the three chlorine isotopomers present in the sample in natural abundances and two weaker Q branches belonging to the first hot bands of the two more abundant isotopomers, ³⁵Cl₂ and ³⁵Cl³⁷Cl, have been observed. Lines with values of J up to 60 for the fundamentals and 50 for the hot bands have been measured in these fully resolved structures. Some additional lines belonging to O and S branches of the fundamentals and hot bands have also been recorded. The analysis of these data has rendered a new and more precise set of rotational molecular constants and band origins for the first three vibrational states of the chlorine isotopomers.     

Spontaneous emission of photons and electrons during chemisorption of chlorine on sodium

Photons and electrons are emitted when Cl₂ molecules react on a Na surface prepared by UHV evaporation. The emission yield per reacting molecule is 10^?7-10^?6 for photons and approximately 10^?5 for electrons. The dominating light emission band has a maximum at hv = 2.15 eV (width 0.6 eV). A less intense u.v. band has a maximum at about 4.7 eV. A drastic decrease in the photon and electron emission at a Cl₂ exposure of about 5.10^?3 torr·sec, is attributed to the formation of a continuous NaCl film on the Na surface.