Reaktionen silylierter Phosphanimine mit Iodmonochlorid und Iodtrichlorid. Die Kristallstrukturen von [Me3SiNPMe3 · ICl], [Ph3PNCl · ICl] und [Me3PN(H)PMe3] [ICl2]2

Reactions of Silylated Phosphorane Imines with Iodine Monochloride and Iodine Trichloride. The Crystal Structures of [Me₃SiNPMe₃ · ICl], [Ph₃PNCl · ICl], and [Me₃PN(H)PMe₃][ICl₂]₂ The donor-acceptor complex [Me₃SiNPMe₃ · ICl] has been prepared from Me₃SiNPMe₃ and ICl in acetonitrile solution forming yellow-orange crystals. [Ph₃PNCl · ICl] can be prepared by the reaction of Me₃SiNPPh₃ with ICl₃ in dichloromethane solution forming pale yellow crystals. [Me₃PN(H)PMe₃][ICl₂]₂ is formed in a small amount by a slow reaction of Me₃SiNPMe₃ with ICl₃ in CCl₄ suspension in the presence of traces of moisture. All samples are characterized by IR spectroscopy and by X-ray structure analyses. [Me₃SiNPMe₃ · ICl] (1) : Space group Iba2, Z = 8, structure solution with 1 727 observed unique reflections, R = 0.051. Lattice dimensions at ?60°C: a = 1 510.7, b = 1 862.8, c = 988.9 pm. 1 has a molecular structure in which the N atom of the phosphorane imine is connected with the iodine atom of the ICl molecule in a linear arrangement N? I? Cl. Bond lengths N? I = 222.7 pm, I? Cl = 265.1 pm. [Ph₃PNCl · ICl] (2) : Space group Pna2₁, Z = 4, structure solution with 1 530 observed unique reflections, R = 0.030. Lattice dimensions at 20°C: a = 1 522.8, b = 1 408.3, c = 865.8 pm. 2 has a molecular structure in which the N atom of the N chlorophosphorane imine is connected with the iodine atom of the ICl molecule in a linear arrangement. Bond lengths N? Cl = 174.4 pm, N? I = 229.5 pm, I? Cl = 251.2 pm. [Me₃PN(H)PMe₃][ICl₂]₂ (3) : Space group P2₁/c, Z = 4, structure solution with 1 989 observed unique reflections, R = 0.029. Lattice dimensions at ?50°C: a = 1 223.1, b = 1 090.2, c = 1 482.8 pm, β = 112.21°. 3 consists of [Me₃PN(H)PMe₃]²⁺ ions and ICl₂^? anions. The PNP bond angle of the dication amounts to 134.4° with PN distances of 165.6 and 166.1 pm, approximately according to double bonds.     

31P CP-MAS NMR,Vibrational, and X-Ray Characterization of the Adducts of Triphenylphosphine Sulfide with ICl and IBr

The reactions between triphenylphosphine sulfide (Ph₃PS) and ICl in CCl₄ and IBr in CH₂Cl₂ in 1 : 1 molar ratio give the solid adducts Ph₃PS · ICl ( I ) and Ph₃PS · IBr ( II ) whose structures have been solved by X-ray diffraction. Compounds I and II consist of discrete molecule units and feature the S–I–Cl or S–I–Br linear group. The S–I bond distances in I , II (2.641(1), 2.665(1) Å respectively) and in compound 2 Ph₃PS · 3 I₂ ( III ) (2.729(2) Å) are correlable to the net increase in the I–X (X = Cl, Br, I) bond distance. The structural features of I , II and III are in accordance with ³¹P CP–MAS NMR, FT-Raman and FT-IR spectral data, and elucidate the nature of the donor (Ph₃PS)-acceptor (ICl, IBr, I₂) interaction.     

Angle and bond-length dependent C6 coefficients for H2 interacting with H,Li, Be and rare gas atoms

Summary Accurate new C₆ dispersion energy coefficients, and their dependence on the diatom orientation and bond length, are calculated for molecular hydrogen interacting with an atom of H, Li, Be, He, Ne, Ar, Kr or Xe. They are generated from accurateab initio pseudo dipole oscillator strength distributions (DOSD) for H₂, H, He and Be, and reliable semiempirical ones for Li, Ne, Ar, Kr and Xe. Compact power series expansions for the diatom bond-length dependence of these coefficients, suitable for incorporation into representations of full potential energy surfaces for these systems, are determined and assessed.     

Vibrational relaxation dynamics of I35Cl(B, v') induced by low-temperature collisions with He atoms

Using laser-induced fluorescence and two-laser, pump-probe spectroscopy, collision-induced vibrational relaxation is observed to compete with the dissociation of electronically excited ICl in a helium carrier gas expansion. By thoroughly characterizing the expansion properties, we observe that collisions of ICl(B, v'= 3) molecules with He atoms in the expansion induce vibrational relaxation of the initially prepared dihalogen down to rotor states in the next lower ICl(B,v'= 2) level on timescales that compete with the rate for non-adiabatic transfer from the B state to the Z1 state. The resulting ICl(B,v'= 2,j') product rotational distribution, along with the analogous ICl(B,v'= 1,j') distribution formed by collisional relaxation of molecules in the long-lived ICl(B,v'= 2) level are compared to ICl(B,v'= 2,j') products formed by vibrational predissociation of He...ICl complexes prepared in different intermolecular vibrational levels within the He + ICl(B,v'= 3) potential. No evidence is observed for resonance-enhanced collisional cross sections, even at the low temperatures achieved, T < 1.0 K.     

∧-related Quantum Interference of ^2П [Case（a）] Diatom on Rotational Energy Transfer

To study theoretically the relationship between the integral interference angle and the scat- tering angle in collisional quantum interference, the integral interference angle of atom- ^2П[case（a）] diatomic molecules system is described. To simulate the experiment theoretically, the theoretical model on collision-induced rotational energy transfer in an atom- ^2П[case（a）]diatom system is presented based on the first order Born approximation taking into account of the long-range interaction potential. For the ^2П electronic state in the Hund＇s case（a） diatom, the degree of the interference is discussed. The interference angles of collision-induced rotational energy transfer of CN（A^2П） in Hund＇s case（a） with He, Ne, and Ar are calculated quantitatively. The key parameters in the determination of integral interference angles are obtained.     

Measurements of the hyperfine dimer spectrum for H2-Ne,H2-Ar,H2-Kr by the magnetic beam renosance technique

Measurements are performed on ortho H₂(I = 1, j = 1, vibrational ground state)-X dimers with X = Ne, Ar, Kr; the dimers H₂-X occur in their van der Waals stretch ground state. The dimer end-over-end rotational states (quantum number L) are investigated for L ?2. The rf hyperfine-transition frequencies are measured, 30 ? v ? 600 kHz. Combining our results with scattering data from the Göttingen group, for H₂Ne the full potential could be described with high accuracy. For the other systems, a simple molecular parameter is derived pertaining to the dimer system. As our spectroscopy mainly permits a sensitive probing of the well region, new scattering data are needed to determine accurate model potentials over the full range.     

Iodine monochloride as a thermal source of chlorine atoms: The reaction of chlorine atoms with hydrogen

The use of iodine monochloride (ICl) as a thermal source of chlorine atoms in known concentration is discussed with particular reference to the suppression, by large excesses of iodine, of the chain processes normally associated with chlorine atom reactions. The kinetics and mechanism of the reaction of ICl with hydrogen are presented in a study covering the temperature range 205–337°C, and the pressure ranges: ICl, 6–20 torr; I₂, 3–13 torr; and H₂, 9–520 torr. The reaction, followed spectrophotometrically in a static system, is shown to be homogeneous, first order in ICl and in H₂, and inverse half-order in I₂, over several half-lifetimes of the ICl, yielding HCl as the sole product. The rate data obtained in this work for the reaction are combined with the critically evaluated results of other workers in an Arrhenius plot covering the temperature range 286–730°C, and three orders-of-magnitude in the rate constant, yielding the results, log k₁/(1/mole sec) = 10.68–5.26/θ, where θ = 2.303RT in kcal/mole. This value of k₁ is lower by a factor of about two than that proposed in a recent review by Fettis and Knox, and is clearly at variance by a factor of two or more with the most recent data of Clyne and Stedman.     

Collisional de-excitation of the metastableD-states of Ba+ by He,Ne, N2 and H2

The rate constants 〈σ · υ〉 for collisional de-excitation of the metastable 5D states of Ba⁺ ions have been determined in an ion trap experiment. TheD-states are selectively populated by pulsed laser excitation of the 6P _1/2 or 6P _3/2 state and the decay at different background pressures is monitored by the change in fluorescence intensity of the excited ions. From the pressure dependence of the decay constants we calculate the de-excitation rate constants for different collision partners, averaged over the velocity distribution of the trapped ion cloud. For He, Ne, H₂ and N₂ we obtain in the c.m. energy range of 0.1–0.5 eV: 〈σ·υ〉 (He)=3.0±0.2·10^?13cm³/s, 〈σ·υ〉 (Ne)=5.1±0.4·10^?13cm³/s, 〈σ·υ〉 (H₂)=3.7±0.3·10^?11cm³/s, 〈σ·υ〉 (N₂)=4.4±0.3·10^?11cm³/s. The results can be understood qualitatively by a consideration of the ion-atom and ion-molecules interaction potential.     

Applications of carbon-13 resonance spectroscopy—XV : The degenerate cope-rearrangement of bullvalene

The temperature dependence of the ¹³C-NMR spectrum of bullvalene has been studied from ?67 to +128°C using fourier transform spectroscopy and ¹H broadband decoupling. Lineshape analysis based on the Anderson-Kubo-Sack theory yielded E_a=13·9±0·1 kcal/mole, log A= 14·0±0·1, ΔH3 = 13·3±0·1 kcal/mole, and ΔS3 = 3·4±0·4 e.u. The pertinent features of dynamic ¹³C-NMR spectroscopy are discussed.     

Measurements of inelastic cross sections for the (j,m) = (2,0)→(3,0) rotational transition of CsF in collisions with atoms and molecules

Individual state-to-state rotational transitions have been resolved in small angle scattering of polarized CsF molecules on Ne, Ar, C₂, H₆, N₂, CO, CO₂, CHF₃ at center of mass energies of about 0.1 eV. The absolute inelastic cross sections range from 5Ų up to 600Ų.     

The dipole moment in the lowest singlet pi formed from pi state of indole determined by the optical Stark effect

Abstract— A Stark effect is observed in the rotational fine structure of the 0–0 band of the lowest π*π state of indole. This yields a dipole moment change |Δμ_A| = 0·14±0·05. D. Evidence is presented which indicates that the sign of Δμ_A is positive. An increase of dipole moment on excitation is in agreement with the value (+ 0·06 D) corresponding to the previously calculated orbitals of Song and Kurtin. The direction of the transition moment, calculated from the results of rotational analysis published by Mani and Lombardi, is found to be 26° from the molecular A-axis.     

Silica‐supported ICl as a novel heterogeneous system for the rapid oxidation of urazoles to triazolinediones

ICl–SiO₂ as a new reactive system was prepared by the treatment of iodine monochloride with an activated silica gel in chloroform. ICl–SiO₂ in a heterogeneous system efficiently oxidized urazoles to the corresponding triazolinediones under mild conditions in high yields at room temperature. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:389–393, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20444     

Rovibrational structures in floppy triatomics: distributed gaussian functions treatment for the Ne2H- system

The full sequence of the bound states for a very floppy triatomic complex, Ne2H- in its ground electronic state, are initially computed for the rotationless situation and employing a variational approach that expands the total nuclear wave function over a large set of symmetry-adapted, distributed Gaussian functions and employs accurate atom-atom potential energy data. The results are tested for numerical convergence, compared with the behavior of both its diatomic fragments, Ne2 and NeH-, and further compared with the results for the Ne3 case. The computational analysis is extended to the production of the rotational constants for the very nonclassical ground state vibrational configuration by making use of the previous findings. The method is shown to provide us with several illuminating details on the nanoscopic internal dynamics of this very weakly bound quantum aggregate.     

Microwave—optical double resonance in the B 3Π0+ excited state of ICl

Pure rotational transitions were observed in the electronically excited state B ³Π₀⁺ of ICl. This state was populated by optical pumping with a single-mode dye laser. From the observed spectrum precise values of the quadrupole hyperfine coupling constant cqQ of iodine and the effective rotational constant were derived for both isotopes I ³⁵Cl and I ³⁷Cl.     

Classical rotational and centrifugal sudden approximations for atom—molecule collisional energy transfer

The application of centrifugal and rotational sudden approximations to classical trajectory studies of rotational energy transfer in atom—molecule collisions to examined. Two different types of approximations are considered: a centrifugal sudden (CS) approximation, in which the orbital angular momentum is assumed to be constant during collisions, and a classical infinite order sudden (CIOS) approximation, in which the CS treatment is combined with an energy sudden approximation to totally decouple translational and rotational equations of motion. The treatment of both atom plus linear and nonlinear molecule collisions is described, including the use of rotational action-angle variables for the rotor equations of motion. Applications of both CS and CIOS approaches to rotational energy transfer in He + I₂ collisions are presented. We find the calculated CS and CIOS rotationally inelastic cross sections are in generally good agreement [errors of (typically) 10–50%] with accurate quasiclassical (QC) ones, with the CS results slightly more accurate than CIOS. Both methods are less accurate for small |Δj| transitions than for large |Δj| transitions. Computational savings for the CS and CIOS applications is about a factor of 3 (per trajectory) compared to QC. We also present applications using the CS method to rotational energy transfer in He, Ar, Xe + O₃ collisions, making comparisons with analogous QC results of Stace and Murrell (SM). The agreement between exact and approximate results in these applications is generally excellent, both for the average energy transfer at fixed impact parameters, and for rotationally inelastic cross sections. Results are better for He + O₃ and Ar + O₃ than for Xe + O₃, and better at low temperatures than at high. Since SM's quasiclassical treatment considered only total internal energy transfer without attempting a partitioning between vibration and rotation, while our CS calculation considers only rotational energy transfer, the observed good agreement between our and SM's cross sections indicates that most internal energy transfer in He, Ar, Xe + O₃ is rotational. The relation of this result to models of the activation process in thermal unimolecular rate constant determination is discussed.     

Experimental determination of level shift and broadening by predissociation of the B3Π0· state of ICl

From the semiclassical analysis of the coupling between discrete molecular levels and continuum levels simple relations for the level shift and the level broadening are known. Laser spectroscopy on the transition is B³Π₀·?X¹Σ⁺ is applied to demonstrate the overall validity of these relations in the rotational ladder of the vibrational state υ′ = 3 of B³Π₀·. Deviations for low rotational quantum numbers might be attributed to the still unresolved hyperfine structure and the possible hyperfine predissociation and for very large rotational quantum numbers to the distortion through a coupling with a second continuum.     

Theoretical interpretation of infrared spectra of the Cl?H stretching vibration in the gaseous (Ch3)2O · · · HCl complex

The paper presents a theoretical interpretation of the fine structure of infrared spectra of the Cl? H stretching region in the gaseous (CH₃)₂O ··· HCl complex. The idea of Millen and Schrems is adopted, in which the spectrum represents a vibrational progression of the hydrogen-bond stretching mode, and each subband is formed by the progression of the hydrogen-bond bending mode. The rotational structure is present in such defined fine bands. Theoretical bands are calculated for three different temperatures and for the complex with DCl using two coupling parameters evaluated from the bandwidth. Results show that the most intense peak is associated with the Oσ ← Oσ transition in the stretching O ··· Cl vibration. They also suggest that the complex is nonplanar.     

An ab initio-based global potential energy surface for the SH3 system and full-dimensional state-to-state quantum dynamics study for the H2 + HS → H2S + H reaction

An accurate potential energy surface for the ground electronic state of SH₃ system has been constructed with 41,882 high level ab initio energy points and the neural network fitting method. The time-dependent wave packet method has been used to calculate the first state-to-state differential cross sections for the title reaction up to 1.2 eV in full dimensions, based on the reactant–product decoupling scheme. It is found that the majority of H₂S are produced in the ground vibrational state, with a large fraction of available energy for the reaction ending up as product translational motion. The differential cross sections at the threshold energy are dominated by a very narrow peak in the backward direction. With the increase of collision energy, the width of the angular distribution increases considerably, which is a typical feature of a direct reaction via abstract mechanism, similar to the H₂ + OH → H₂O + H reaction. © 2018 Wiley Periodicals, Inc.     

Diffusion technique for the generation of gaseous halogen standards

Halogens are known to play an important role in the tropospheric ozone-depletion chemistry and are of special interest because of their influence on the atmospheric oxidation capacity. In this paper, we investigate the application of a capillary diffusion technique for the generation of gaseous halogen standards like Br₂, IBr, ICl and I₂. The influence of capillary dimension (i.e. length and inner diameter), ambient pressure and headspace volume of the diffusion vessel on the test gas output has been evaluated. The experimental output rates are determined from the mass loss of the analyte vessel on a regular schedule and compared with their respective theoretical predictions. We also demonstrate that a 1,3,5-trimethoxybenzene-coated diffusion denuder is capable of collecting gaseous ICl quantitatively, which provides an attractive alternative for the rapid determination of the output of test gas devices. The output rates of ICl measured by the denuder method are in close agreements with the data obtained by the gravimetric method.     

Laser-induced fluorescence spectroscopy of ionic clusters between organic cations and inert gases

The Laser-induced fluorescence spectra of ionic cluster C₆F₆⁺·X_n, where X = He, Ne, or Ar, are obtained by multiphoton ionization of C₆F₆ seeded in an inert gas expansion. Spectral information concerning the red-shifts and linewidths of the ionic cluster are reported and observations relevant to their formation mechanisms are offered.