7791-21-1Relevant articles and documents
On the high-resolution HeI photoelectron spectrum of Cl2O
Motte-Tollet,Delwiche,Heinesch,Hubin-Franskin,Gingell,Jones,Mason,Marston
, p. 452 - 458 (1998)
The high-resolution HeI (58.4 nm) photoelectron spectrum of dichlorine monoxide, Cl2O, has been recorded in the region of the four lowest-energy ionic electronic states. Formation of the ion in its ground and excited electronic states is accomp
Kinetics of the ClO + NO2 + M Reaction
Molina, Mario J.,Molina, Luisa T.,Ishiwata, Takashi
, p. 3100 - 3104 (1980)
The ClO + NO2 + M reaction has been studied with two techniques: Fourier transform infrared spectroscopy of the products, and flash photolysis-ultraviolet absorption to monitor the decay of ClO in excess NO2.The measured third-order rate constant is 1.5E-31 cm6 molecule-2 s-1 at 298 K with M=N2, in good agreement with previous literature values, but the rate constant appears to decrease by up to a factor of 3 in the presence of increasing amounts of OClO.For the infrared studies a stoichiometric mixture of ClO and NO2 was prepared in a flow system by mixing NO with OClO; at least as much NO2 as ClONO2 was produced under a variety of experimental conditions.These two sets of results are incompatible with the assumption made in previous kinetic studies that ClONO2 is the only recombination product; other isomers such as OClONO or ClOONO are likely to be formed three to four times faster.These results imply that potential stratospheric ozone depletion due to chlorofluoromethanes may be even larger than previously thought.
Kinetic and Mechanistic Study of X + ClOCl -> Products (X = Br, Cl, F, O, OH, N) over the Temperature Range 240-373 K
Stevens, Philip S.,Anderson, James G.
, p. 1708 - 1718 (1992)
The rate constants for the reactions of X + ClOCl -> products for X = Br, Cl, F, O, OH, and N have been measured over the temperature range 230-400 K.The rate constants are (in units of cm3 molecule-1 s-1) as follows: (2.1 +/- 0.2) x 10-11 exp for Br + ClOCl; 6.0 +/- 0.6) x 10-11 exp for Cl + ClOCl; (1.5 +/- 0.5) x 10-10 exp for F + ClOCl; (1.3 +/- 0.8) x 10-11 exp for O + ClOCl; (1.7 +/- 0.8) x 10-12 exp for OH + ClOCl; and k298 -15 for N + ClOCl.The rate constants for X = Br, Cl, F, and N are found to correlate with the electron affinity of the attacking radical, suggesting that the mechanism for these reactions involves the partial transfer of an electron from ClOCl to X, and the activation energy for reaction is determined by the ability of the transition state to accommodate the shift in electron density.This trend is similar to that found for a number of non-hydrogen abstraction reactions (X + ClNO, O3, Cl2), where the reactivity scales with the quantity IP(molecule) - EA(radical), where IP refers to the ionization potential and EA the electron affinity.The reactions of O and OH with ClOCl are significantly faster than predicted by the trend, suggesting that the electron-transfer mechanism is not the only driving force in these reactions, which may involve long-range attractive forces leading to stable intermediates.
The ultraviolet photodissociation of Cl2O at 235 nm and of HOCl at 235 and 266 nm
Tanaka, Yoshiki,Kawasaki, Masahiro,Matsumi, Yutaka,Fujiwara, Hisashi,Ishiwata, Takashi,Rogers, Leon J.,Dixon, Richard N.,Ashfold, Michael N. R.
, p. 1315 - 1323 (1998)
The primary photochemistry of gas phase dichlorine monoxide (Cl2O) and of hypochlorous acid (HOCl) following excitation at 235 nm has been investigated using photofragment ion imaging to obtain the recoil velocity and angular distributions of the ground (2P3/2) and spin-orbit excited (2P1/2) atomic chlorine products. In the case of Cl2O, both Cl spin-orbit products exhibit angular distributions characterized by an anisotropy parameter, β=1.2±0.2, consistent with previous interpretations of the ultraviolet (UV) absorption spectrum of Cl2O which associate the broad intense absorption feature peaking at λ～255nm with excitation to a (bent) dissociative state of 1B2(C2v) symmetry. The recoil velocity distributions of the two Cl spin-orbit products are markedly different. The ground state atoms (which constitute >90% of the total Cl atom yield) are partnered by ClO fragments carrying significantly higher average levels of internal excitation. The slowest Cl atoms are most readily understood in terms of three body fragmentation of Cl2O to its constituent atoms. These findings are rationalized in terms of a model potential energy surface for the 11B2 state, which correlates diabatically with ClO(X) radicals together with a spin-orbit excited Cl atom, with efficient radiationless transfer to one (or more) lower energy surfaces at extended Cl-O bond lengths accounting for the dominance of ground state Cl atom fragments. The image of the ground state Cl atoms resulting from photolysis of HOCl at 235 nm is consistent with parent excitation via a transition for which the dipole moment is closely aligned with the Cl-O bond, followed by prompt dissociation (β=1.7±0.2) with the bulk of the excess energy partitioned into product recoil. Such conclusions are consistent with the results of laser induced fluorescence measurements of the OH(X) products resulting from 266 nm photodissociation of HOCl which reveal OH(X) products in both spin-orbit states, exclusively in their zero-point vibrational level, and carrying only modest levels of rotational excitation (well described by a Boltzmann distribution with Trot～750±50K).
Anbar et al.
, p. 1816 (1959)
Dissociation pathways in low energy (0-2 eV) electron attachment to Cl2O
Sailer, Wolfgang,Tegeder, Petra,Probst, Michael,Drexel, Herwig,Grill, Verena,Scheier, Paul,Mason, Nigel J.,Illenberger, Eugen,M?rk, Tilmann D.
, p. 471 - 478 (2001)
Dissociative electron attachment (DA) to ClOCl is studied in a high resolution crossed beam experiment. Two complementary ion pairs, Cl-/ClO- and O-/Cl2-, are observed. The Cl-/ClO- pair arises from a simple Cl-OCl bond cleavage with the electron sitting on either of the two fragments. The O-/Cl2- pair is formed by a concerted reaction with the expulsion of O- (or O) and formation of Cl2 (or Cl2-). Ab initio calculations indicate that in low energy electron attachment an electronically excited state of the precursor anion (ClOCl-* (2B2)) is involved.
MnO3Cl, isolation and crystal structure
Spandl, Johann,Supel, Joanna,Drews, Thomas,Seppelt, Konrad
, p. 2222 - 2225 (2008/10/09)
MnO3Cl is prepared from KMnO4 und ClSO3H. The thermally very unstable compound is identified by its Raman spectrum and a single crystal structure determination: a = 715.4(5), b = 1008.3(7), c = 500.9(4) pm, space group CmC
