The effect of internal excitation on the collision induced dissociation of I+2(2Πg,υ) ions

Cross sections for collision induced dissociation of 0.65 to 3.2 keV I⁺₂(²Π_g, υ) ions in I⁺₂(²Π_g, υ) + N₂(X ¹Σ⁺_g, υ = 0) interactions have been determined. Reaction cross sections for I⁺₂(²Π_{$\text{3}\text{2}$,g}, υ) ions in low vibrational levels vary smoothly from 6 to 10 A² with increasing kinetic energy. Dissociation cross sections for I⁺₂(²Π_{$\text{1}\text{2}$,g}, υ) ions are larger than those involving ground state ions. Processes involving highly excited metastable states of I⁺₂ are not observed in this investigation.     

Effect of inorganic aqueous anions on the synergic extraction of cadmium and zinc with 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one (HPMBP) and lipophilic ammonium salts

As a part of a systematic study of the synergic extractions of metals with mixtures of acidic chelating extractants and lipophilic anion-exchangers (B, X with X^?6 inorganic anion), the extractions of M  Cd and Zn from perchlorate, nitrate and sulphate media with 1-phenyl-3-methyl-4-benzoyl-pyrazol-5- one (HL) and tri-n-octylammonium salts (TOAH.X) or aliquat 336 (TOMA.X) in toluene have been investigated. Three key equilibria describe the extractions: (a) M²⁺+2$\text{HL}$?$\text{ML}{}_2$+2H⁺. (b) $\text{B.X}$ +$\text{HL}$?$\text{B.L}$+H⁺+X^? with B efficiency TOMA < TOAH and X efficiency ClO₄ < NO₃ < SO₄. (c) $\text{ML}{}_2$+$\text{B.L}$?$\text{B.ML}{}_3$ with B efficiency toma > TOAH and Ni ～ Co > Cd > ZN.As a consequence of the conflicting orders of efficiencies of TOMA and TOAH in equilibria b and c, TOAH.X is a better synergic extractant from perchlorate medium than TOMA.X whereas the inverse is observed from nitrate and sulphate media. Equilibrium c is independent of the inorganic anions. Constants of equilibria a, b and c are given. B.ML₃ species are not extracted in 1-octanol.     

Fluorescence quantum yields and cascade-free lifetimes of state selected CO+2, COS+, CS+2 and N2O+ determined by photoelectron—photon coincidence spectroscopy

The details and principles of an apparatus built for measurements of fluorescence quantum yields and cascade-free lifetimes of open-shell cations are reported. These rely on the detection of coincidences between energy selected photoelectrons and undispersed photons. The results of such measurements for CO⁺₂, COS⁺, CS⁺₂ and N₂O⁺ in selected vibrational levels of their excited states are presented. Non-unity fluorescence quantum yields are found for some vibronic levels of CO⁺₂($\text{B}$), COS⁺ ($\text{A}$), N₂OP⁺($\text{A}$) and a non-exponential decay is observed for CS⁺₂($\text{A}$). The data yield the following values for the radiative lifetimes: CO⁺₂($\text{A}$) 124 ± 6 ns, CO⁺₂($\text{B}$) 140 ± 7 ns, COS⁺($\text{A}$) 550 ± 50 ns and N₂O⁺($\text{A}$) 240 ± 12 ns.     

Selected fluorescence and dissociation lifetimes on N2O+ in its Ã(2Σ+),000 and 100 states

Radiative and radiationless lifetimes together with the quantum yield towards fluorescence of individual vibronic states of molecular ions can be determined by threshold electron—fluorescence photon coincidence measurements. This method is here applied to the X?²Π_{$\text{3}\text{2,1,2}$} and òΣ⁺ states of N₂O⁺ which were also studied by high resolution photoionization resonance spectroscopy.     

Vacuum-ultraviolet photolysis of XeF2: XeF(B) fluorescence and quenching

Photolysis of XeF₂ with Kr(123.6 nm), Hg(184.9 nm) and CO(160 to 180 nm) resonance radiation gives strong XeF[B($\text{1}\text{2}$)?X²Σ⁺] fluorescence. The two shorter wavelengths also give weak XeF[D($\text{1}\text{2}$)?X²Σ⁺] emission. The XeF(B) vibrational distribution varies with photon energy and with pressure of added buffer gas. The addition of Xe and molecular gases results in quenching of the XeF^* emision. Stern-Volmer plots of the XeF^* emission intensity were used to obtain quenching rate constants for Xe, N₂, CO₂, NF₃ and F₂. The XeF(BX) emission intensity is diminished by ≈ 50% with addition of one atm of Ar.     

Branching ratio for the production of I2Psol12) in the photodissociation of I2

The production of atomic iodine in the ground (²Pfrsol|3/2) and electronically excited (²P$\text{1}\text{3}$) states following laser-induced photodissociation of I₂ the region 425–498 nm was monitored directly by resonance spectroscopy. The branching ratio for iodine atom formation. R = [I(²P$\text{1}\text{2}$)]/[I(²P$\text{3}\text{2}$)], is above 0.5 in the region 495–498 nm in agreement with the recent observation of laser action on the atomic transition at 1315 nm following photolysis of I₂ using a dye laser. The present experiments permitted deconvolution of the I₂ continuous absorption spectrum below 498 into contributions from the B³ Π_o,u → X ¹Σ_g⁺ and ¹Π_tu → X¹σ_g^? transitions.     

Preferential energy transfer from N2(A) to specific energy levels of Cu atoms

Emission spectra resulting from reaction of “clean” N₂(A³ Σ_u⁺) with copper atoms were studied using a flowing afterglow apparatus. The population distribution of the Cu states was calculated from the spectrum; it indicates that Cu atoms are excited by nearly resonant energy transfer processes. N₂(A,v') + Cu(²S_{$\text{1}\text{2}$}) → N₂(X, v) + Cu^* , and that the transfer is most efficient for N₂(A,v') → N₂(X,v) transitions with large Franck-Condon factors. The preferential energy transfer results in population inversion between some of the Cu states.     

Energy transfer processes in reactions of He(2 3S) and Ne(3P0,2) with CS2

A comparative spectroscopic study in the visible and ultraviolet ranges was conducted on the flowing afterglows resulting from the reactions of He(2 ³S) and Ne(³P_0,2) metastables with CS₂. Penning ionization was found to be the predominant energy transfer process. However, electron—ion recombination within the afterglows constitutes a major secondary process and gives rise to the most intense emitting system, CS(A ¹ Π → X ¹Σ⁺). Both afterglows were found to produce the CS⁺₂($\text{B}$²Σ⁺_u-$\text{X}$²Π_g), CS⁺₂($\text{A}$²Π_u-$\text{X}$²Π_g) and CS(a ³Π-X ¹Σ⁺) emission systems as well as some atomic sulfur emission lines. Some intensity differences were observed and are interpreted in terms of energetics and the formation mechanisms of the emitting species. A moderately strong CS⁺(A ²Π_i-X ²Σ⁺) emission system was also observed in the ehlium afterglow. In addition, a weak, sharp group of bands in the 390–420 nm range in the helium afterglow has been determined to be due to the presence of a small amount of He⁺ ions. This group of bands consists of two overlapping emission systems and are identified as CS(B ¹Σ⁺ → A ¹Π) and CS⁺(B ²Σ⁺ → A ²Π_i).     

Amino-sulphur-fluorine derivatives as fluoride ion donors: preparation of three- and four-coordinated cations of sulphur (IV) and (VI) [1,2]

Pentacoordinated aminosulphur (IV) trifluorides, R₂N$\text{S}$F₃, (in this paper the lone pair in S(IV)-derivatives is always considered as a ligand) and aminosulphur(VI)-oxidetrifluorides, R₂NS(O)F₃, readily lose a fluoride ion to Lewis acids (AsF₅, SbF₅, BF₃) to give sulphur-containing cationic species [R₂N$\text{S}$F₂]⁺ and [R₂NS(O)F₂]⁺ with tetracoordinated sulphur. Tetracoordinated neutral dialkylaminosulphur(IV)-oxidefluorides, R₂N$\text{S}$(O)F, and amino-imino sulphur(IV)fluorides, R₂N$\text{S}$(=NR_f)F, give three-coordinated sulphur cations [R₂N$\text{S}$O]⁺] or [R₂N$\text{S}$NR_f]⁺.The three-coordinated sulphur(VI)cation [R₂NS(O)NR]₊ has also been formed.     

Microwave-optical double resonance in molecular ions. Co+

Microwave—optical double resonance signals have been detected in a mass-selected ion-beam spectrometer for ¹²C¹⁶O⁺. With the optical excitation of fluorescence from the R₁ ($\text{1}\text{2}$) line of the (0,0) band of the A²Π_{$\text{3}\text{2}$} ← X²∑ transition of 20350.6 cm^?1, the microwave resonances occurred at 118101.8 ± 0.2 MHz and at 117694 ± 2 MHz corresponding to the N= 1, J = $\text{3}\text{2}$ ← N = 0, J = $\text{1}\text{2}$ and the N = 1, J = $\text{1}\text{2}$ ← N = 0, J = $\text{1}\text{2}$ transitions.     

Metal chelates of 1-acetylpyridinium chloride-4-phenyl-3-thiosemicarbazide

The metal chelates of 1-acetylpyridinium chloride-4-phenyl-3-thiosemicarbazide [(APTS)]⁺Cl^? of the type [M(APTS)X₂]⁺ Cl^? (M = Co(II), Ni(II), Cu(II), Zn(II) or Cd(II); X = Cl, Br or $\text{1}\text{2}$SO₄) have been prepared and characterized on the basis of elemental analysis, molar conductance, IR, electronic spectra and magnetic studies. IR spectral studies showed that the ligand coordinates via thioketo and NLH groups. Magnetic and spectral studies suggest a tetrahedral structure for Ni(II), pseudo-tetrahedral for Co(II) and square planar and/or distorted tetrahedral for Cu(II) chelates.     

An electrical conductivity (EC) study of the thermal dissociation of [Co(NH3)6]X3 and [Co(en)3]X3 complexes

The thermal dissociation of the [Co(NH₃)₆]X₃ (X = Cl^?, Br^?, I^?, and NO^?₃), [Co(en)₃]X₃ (X = Cl^?, Br^?, I^?, NO^?₃, HSO^?₄ and $\text{1}\text{2}$ C₂O^2?₄), cis- [Co(en)₂Cl₂]Cl, and trans-[Co(en)₂ClBr]NO₃ complexes was investigated by an electrical conductivity (EC) technique. During the thermal dissociation reactions, liquid or semi-liquid phases are formed which cause large increases in the EC of the compound. The effect of concentration of the complex in a matrix medium as well as the composition of the matrix material on the EC curves were also determined.     

Synthesis of triphenylphosphonopropionbetainetriorganotin(IV) salts [(C6H5)3P(CH2)2CO2SnR3]+X−, by nucleophilic displacement of anions from triorganotins

Trimethyl- and triphenyl-tin(IV) hydroxide act on triphenyl(2-carboxyethyl)-phosphonium hydrochloride, which is made from 3-chloropropionic acid and triphenylphosphine, to release water in the presence of dimethylformamide (DMF) as a catalyst. The water is azeotropically distilled to drive the reaction forward and produce triphenylphosphonopropionbetainetrimethyl- and triphenyl-tin(IV) chlorides in high yield. The latter product also results from the displacement of chloride from triphenyltin(IV) chloride by the phosphobetaine, (C₆H₅)₃P(CH₂)₂CO₂, which is made by treating the phosphonium hydrochloride with bicarbonate, and the compounds [(C₆H₅)₃P(CH₂)₂CO₂Sn(C₆H₅)₃]⁺X^? where X = Cl, Br, I, N₃, NCS, NO₃, B(C₆H₅)₄ and Co(CO)₄ are made in the same way. The acetate salt results from metathesis from the chloride and lead(II) acetate. A double salt, [(C₆H₅)₃P(CH₂)₂CO₂SnR₃]⁺ [R₃SnX₂]^?, is formed for X = Cl, Br and N₃ by adding additional (C₆H₅)₃SnX to the already-formed simple salts. Double salts are also obtained from the $\text{1}\text{1}$ reactions between the phosphobetaine and triphenyltin(IV) isocyanate and methyldiphenyltin(IV) chloride. The phosphonium chloride double salt could be converted to the thiophosphonium derivative by heating with elemental sulfur in ethanol. The products of these novel nucleophilic displacement reactions are high melting solids. Tin-119m Mössbauer data are consistent with five-coordinated, triorganotin(IV) formulations with the exception of the diphenyl(8-hydroxyquinolinato)tin(IV) chloride salt in which the tin atom is six-coordinated, and the diphenyltin system cis-oriented. The parameters otherwise do not change with the nature of the X group, which is the tetracarbonylcobaltate derivative is tetrahedral by infrared, establishing the ionicity of the products. The chloride exhibits a molar conductivity indicative of a $\text{1}\text{1}$ electrolyte in DMF. A bridging acetate structure in the solid is consistent with the lowered ν(CO₂) frequencies. The Mössbauer spectra of the double salts give simple doublets of lowered isomer shift (IS) and raised quadrupole splitting (QS) which may arise from a cross-linking ion pairing of the polymer chains in the solid, and the NMR spectra of the two methyltin derivatives shows only a single resonance line and tin satellites which is rationalized by a dynamic exchange process. The products are formulated as associated in carboxylate polymers with dangling triphenylphosphonium cations.     

Extraction of cobalt(II) and nickel(II) with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one (HPMBP) and tri-n-octylamine (TOA)

The extraction of Co(II) with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one ((H)PMBP) and tri-n-octylamine (TOA) is investigated in order to explore the influence of diluents and inorganic anions with synergistic acidic extractant + liquid anion exchanger systems. Although it is proved that the same species [HTOA]⁺ [Co(PMBP)₃]^? is extracted from various inorganic media, with toluene as the diluent, the presence of ClO₄^? SO₄^2? or Cl^? anion modifies the distribution of the anions which are associated to (HTOA)⁺ in the organic phase, leading to different synergistic equilibria; with Cl^? or SO₄^2?: $\text{CO(PMBP)}{}_2$ + $\text{(HTOA}{}^{\mathrm{+}}$,PMBP^?) ?$\text{(HTOA}{}^{\mathrm{+}}$,Co(PMBP)₃^? (log K = 6.10) and with ClO₄^? : $\text{Co(PMBP)}{}_2$ + $\text{HPMBP}$ + $\text{(HTOA}{}^{\mathrm{+}}$,ClO₄^? ? $\text{(HTOA}{}^{\mathrm{+}}$,Co(PMBP)₃^? + H⁺ + ClO₄^? (log K = 2.34) The same synergistic equilibrium is observed for the extraction of Ni(II) from ClO₄^? medium, with a comparable value of the constant (log K = 2.45). The synergistic effect is cancelled in n-octanol.     

Theoretical study of the 12A″ (X2II) State of N2 O+: implications for isotopic scrambling

Ab initio calculations suggest that the potential energy surface for the 1²$\text{A}$″ state of N₂O⁺ has a secondary minimum corresponding to a strongly bent structure. This structure is computed to lie below the $\text{A}$²Σ ⁺ state energetically and therefore may be responsible for the isotopic scrambling observed in this energy region.     

Excitation of XeF* by reactions of XeF2 with Ar(3P0,2),Kr(3P2) and Xe(3P2)

The reactions of the lowest metastable states of Ar, Kr and Xe with XeF₂ were studied in a flowing afterglow apparatus; XeF emission (from D²Π_{$\text{1}\text{2}$} and B ²Π⁺ states) was observed in all cases. The total rate constants (cm³ molecule^?1 s^?1) for XeF^* formation were determined as 75 × 10^?11 ? Xe(³P₂);64 × 10^?11 ? Kr(³P₂) and 20 × 10^?11 ? Ar(³P_0,2). The reactions of Ar(³P_0,2) and Kr(³P₂) with XeF₂ also gave ArF^* and KrF^*, respectively. Analysis of these emissions indicates that at least two different mechanisms are operative: reactive quenching by the ionic—covalent curve-crossing mechanism and excitation transfer. The Ar(³P_0,2 + XeF₂ reaction is a sufficiently strong source of XeF(D—X) emission that the main features of the XeF(D²Π_{$\text{1}\text{2}$} ? X²Σ⁺) system could be photographed and tentative assignments of these vibrational bands are given. The XeF(D → B) emission could not be observed and the ratio of the D—X versus the D—B transition probability must be > 1000 : 1.     

Preparation and synthetic utility of fluorinated phosphonium salts,bisphosphonium salts and phosphoranium salts

The synthesis and mechanism of formation of phosphonium salts of the type [R₃$\text{P}\text{+}$CFXY]Z^? (where X = F, Cl, Br; Y = Br, Cl; Z = Br, Cl), $\text{bis}$-phosphonium salts of the type [R₃$\text{P}\text{+}$CF₂$\text{P}\text{+}$R₃]2Br^?, and phosphoranium salts of the type [R₃$\text{P}\text{+}$$\text{C}\text{?}$F$\text{P}\text{+}$R₃]X^? (X = Br, Cl) will be presented. The applicability of these substrates in the generation of useful nucleophilic or electrophilic synthetic intermediates will be discussed.     

X-ray molecular structure of the 1:1 adduct of [FeH(CO)4]− and dimethyl acetylenedicarboxylate. η3-[trans-2,3-bis(methoxycarbonyl)acryloyl]tricarbonylferrate

The crystal structure of a bis(triphenylphosphine)iminium salt of the 1:1 adduct of [FeH(CO)₄]^? and dimethyl acetylenecarboxylate has been determined from three-dimensional X-ray data collected by the counter method. Single crystals belong to the triclinic space space group P$\text{1}$, with two units of [C₃₆H₃₀NP₂]⁺[C₁₀H₇FeO₈]^? in a cell of dimensions: $\text{a}$ = 13.918(2), $\text{b}$ = 15.669(5), $\text{c}$ = 9.909(2) Å, $\text{α}$ = 91.22(3), $\text{β}$ = 94.83(2), and $\text{γ}$ = 77.62(2)°. The structure was refined to a conventional $\text{R}$ of 0.068 for 5373 observed

reflections. The resulting structure indicates that the complex anion is η³-[$\text{trans}$-2,3-bis(methoxycarbonyl)acryloyl]tricarbonylferrate, the coordination around the iron atom being described as a considerably distorted trigonal bipyramid. A comparison of the present structure with the structures of related complexes suggests that the η³-acryloyl portion is best represented as an intermediate of (η³-allyl) with the oxygen atom and (η²-olefin + η¹-acyl). The short Fe-C(acyl) length of 1.897(5) Å implies an enhanced back-donation of electrons from the iron atom to the acyl group.     

Electric moments,polarizabilities and hyperpolarizabilities for BH(X1Σ+ and CH+ (X1Σ+)

The electric moments and static polarizabilities of BH(1σ²2σ²3σ², X¹Σ⁺) and CH⁺ (1σ²2σ²3σ², X¹Σ⁺) were calculated at the experimental internuclear separation in the LCAO SCF MO approximation. Most of the molecular properties reported in this paper for BH and CH⁺ appear for the first time and should be close to the Hartree—Fock limit. All tensors up to the fourth rank have been included in this study. The isotropy and anisotropy of the α, β and γ tensors are, in atomic units. $\text{α}$ = 22.71, Δα = ?0.26, $\text{β}$ = 55.1, Δβ = ?183.7, $\text{γ}$ = 12428, Δ₁γ = 37895, Δ₂γ = 25120 for BH and $\text{α}$ = 7.73, Δα = 0.39, $\text{β}$ = ?12.4, Δβ = ?11.7, $\text{γ}$ = 344, Δ₁γ = 1515, Δ₂γ = 750 for CH⁺.