Fluorescence lifetimes in BO2 (A2Πu)

Fluorescence lifetimes and fluorescence quenching rates are reported for several vibronic levels in the A²Π_u electronic manifold of BO₂. The relationship of these results to earlier Hanle-effect measurements is discussed.     

Gas phase electron diffraction study of tetravinyltin Sn(CHCH2)4

The tetravinyltin molecule has been studied by gas phase electron diffraction. The r_a structure analysis is based on the assumptions that a single conformer occurs in Sn(CHCH₂)₄ and that tin has a tetrahedral bond configuration. The preferred model (S₄ symmetry) predicts all four vinyl groups to be intermediate between staggered and eclipsed conformations. The structure refinement gives the following parameters (bond lengths, r_a, in nm, valence angles in degrees):

, SnCC = 121.9(0.6), CC = 0.1349(8), SnCH = 116.8(4.5),<C—H?_av. = 0.1098(14). The uncertainties given in parentheses represent three times the standard deviation values.The observed shortening of the

bond in Sn(CHCH₂)₄ from

in SnMe₄ (by 0.0027 nm) is equal to the shortening that occurs on going from

in ethane to

in propylene. With the corresponding Si and Ge derivatives, this effect is less pronounced.     

Laser-induced photodissociation of He+2

The momentum distributions of He⁺ fragments from photodissociation of He⁺₂ ions have been recorded in a crossed-beams experiment. The discrete values of the kinetic energy releases can be predicted from the vibrational spacings in the ground state of the primary ions.     

Carbon-13 nuclear magnetic resonance studies of some phosphonium,arsonium, sulfonium and pyridinium keto-stabilized salts,and ylides and of their palladium(II) complexes

The ¹³C chemical shifts, the ¹³C³¹P coupling constants, and some one-bond ¹³C¹H coupling constants were measured for the title compounds. For the ylides of phosphorus, arsenic and sulfur, the data are consistent with an sp²-hybridized ylidic carbon with a strong, localized negative charge, while for the pyridinium ylide this charge is much more delocalized. in the homologous series of salts the electron-withdrawing ability of the groups studied varies in the order: Ph₃P⁺ < Ph₃As⁺ « Me₂S⁺ « Me₂C₅H₃N⁺. The differences in the carbonyl chemical shift between the ylides and the corresponding salts are a measure of the resonance stabilization of the negative charge in the form X⁺CCO^?; this stabilization varies with the groups studied in the order: Ph₃P⁺ < Ph₃As⁺ ≈ Me₂S⁺ « Me₂C₅H₃N⁺. The ylide—palladium(II) complexes contain a bond between the ylidic carbon and the metal: the ylidic carbon is shifted upfield in the complex with respect to the free ligand, while the adjacent carbonyl is shifted strongly downfield. These data suggest that the PdC(1) bond is strongly polarized with a high electron density on the C(1) atom which cannot be delocalized through resonance as in the free ligands.     

Deuterium isotope effect in the T1 → S0 radiationless transition of propynal in the gas phase

The phosphorescence lifetimes of propynal-h₁ and propynal-d₁ have been measured at room temperature in the 40 mTorr-1 Torr pressure range The reciprocal of the zero-pressure lifetime (k₀) is (3.10 ± 0.05) × 10³ and (1.70 ± 0.04) × 10³ s^?1 for propynal-h₁ and propynal-d¹ For both compounds the rate constant for self-quenching between triplet and ground-state molecules is k_SQ = (1 2±007) × 10³ Torr^?1 s^?1 The deuterium isotope effect is attributed to the T₁ → S₀ radiationlcss decay, for which k^H_ISC/k^D_ISC = 2 4     

Crystal structures and phase transition of Rb2TeBr6 (300-12.5 K)

Using 298 and 160(3) K diffractometer intensity data the structure of Rb₂TeBr₆ has been determined by single crystal X-ray technique and refined to a final R_w of 0.041 and 0.037, respectively (K₂PtCl₆ type structure, space group Fm3m, Z = 4 with a₂₉₈ = 10.773(4) Å and a₁₆₀ = 10.713(6) Å). The powder diffraction pattern from 300 to 12.5 K was recorded by a low-temperature Guinier diffractometer and camera. Below 45(5) K a second-order phase transition leads to a tetragonally distorted structure corresponding to a softening of the T_1g(Γ) rotary phonon. The powder pattern measured with the diffractometer at 12.5 K was used for structural refinement (R = 0.092). This low-temperature phase shows a ferrorotative displacement of the TeBr₆-octahedra with a tilt angle of 4.7(1) deg. (space group $\text{I4}\text{m}\text{, Z = 2, a = 7.4726(3)}$ Å and c = 10.7008(5) Å). The structural results indicate that there is no stereochemical activity of the lone pair electrons at Te(IV) even at very low temperatures. Phase transitions of Rb₂TeBr₆ and Rb₂TeI₆ (A_2g(X)-condensation) are compared. The results of a lattice dynamic calculation shows that only the T_1g(Γ) condensation can be explained with a rigid ion model.     

On m-changes in atom-rigid-rotor collissions: influence of an initial rotation

Reorientation of the angular momentum of a diatomic molecule in collisions with atoms is investigated using classical mechanics. A factorisation formula for cross sections for rotational excitation is given. The factorisation allows the calculation of the state-specific cross section d σ (j′ m′ ← jm)/dΩ once the m-averaged cross sections d σ (j″← 0 )/dΩ for all possible j″ are known. The approach is applied to the Na₂-He system.     

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.     

1H and 13C NRM and infrared spectral studies on mixed ligand complexes of the type cis-[Co(en)2(Im)Cl]Cl2

A number of mixed ligand complexes of the type [Co(en)₂(Im)Cl]Cl₂ (Im = imidazole or a substituted imidazole) have been synthesized by reaction of trans-[Co(en₂Cl₂]Cl with the imidazole ligands. Electrical conductivity measurements support the ionic (1:2) formulation of the compounds, the electronic spectra is in agreement with an octahedral stereochemistry, and the IR and NMR (¹H and ¹³C) spectra strongly favour the cis configuration for the isolated complexes, [Co(en)₂(Im)Cl]Cl₂.Trans-[Co(en)₂Cl₂]Cl reacts with KNCS to form cis-[Co(en)₂(NCS)₂Cl, the crystal structure of which is briefly reported. This lends additional support in favour of the probable cis configuration of the above complexes.     

Studies of gas-phase clusters: the solvation of HNO3 in microscopic aqueous clusters

The formation and stability of aqueous clusters of nitric acid were studied utilizing a free-jet expansion technique, coupled with electron impact ionization mass spectrometry. Evidence for the onset of solvation at very small cluster sizes is presented.     

Esr and endor studies of partially deuterated and chlorinated phenalenyls : New synthetic pathways

A variety of partially chlorinated and deuterated phenalenyl radicals has been produced by the reaction of the respective acenaphthylenes with chloroform as a carbenoid precursor and via thermal decomposition of some mercury carboxylates. By ESR and ENDOR-in-solution measurements the effectiveness of the different reaction paths to specifically substituted compounds has been investigated.     

On Cross Relaxation In Photoexited Triplet States

Variable frequency ODMR experiments on a photoexcited triplet state molecule oriented in a single crystal host have been used to show that an anticrossing exists in the energy level diagram of the guest electron spins plus host nuclear spins at cross relaxation fields. As a consequence, the rate of energy transfer between guest and host is governed by nuclear spin-spin rather than the much slower spin- lattice relaxation. This has been confirmed by a direct measurement of the cross relaxation time (110 μs) in perdeuterobenzophenone in 4,4'-dibromodiphenylether, using microwave pulse techniques.     

Solving the continuum problem of collision-induced dissociation and recombination

The stationary Schrödinger equation with continuum boundary conditions is solved numerically. Quantum probabilities of collision-induced dissociation/recombination for models with two degrees of freedom are calculated using an integral-equation matching procedure together with analytical wavefunctions or finite element solutions alternatively. Model results for He+Ne₂ → He+2Ne are reported.     

5T2-1A1 Spin transition and residual paramagnetism in bis(2,4-bis(2-pyridyl)thiazole)iron(II) complexes: mössbauer effect and magnetism

The ⁵⁷Fe Mössbauer effect in [Fe(pythiaz)₂] (BF₄)₂ (I) and [Fe(pythiaz)₂] (C&O₄)₂ (II) has been studied between 298 and 4.2°K (pythiaz = 2,4-bis(2-pyridyl)thiazole). At 298°K compound I shows a doublet with ΔE_Q(⁵T₂) = 1.29 mm sec^?1 and δ^1S(⁵T₂) = +0.93 mm sec^?1 characteristic of a ⁵T₂ ground state. At 236°K, a second doublet, typical for a ¹A₁ ground state appears. The transition ⁵T₂ å ¹A₁ progresses as the temperature is lowered but levels off below ≈ 120°K. At 4.2°K, 59% of the intensity is due to the ¹A₁ state, and ΔE_Q(¹A₁) = 1.59 mm sec^?1 and δ^1S(¹A₁) = +0.26 mm sec^?1. In an applied magnetic field, V_zz(¹A₁) < 0 has been determined Similar results have been obtained with compound II.Debye-Waller factors f5_T2 and f1_A1. were determined from the Mössbauer spectra under the assumption of Curie-Weiss dependence of the magnetism for the ⁵T₂ and constant μ_eff for the ¹A₁ ground state. The resulting temperature dependence of f1_A1 is highly unusual thus suggesting complicated magnetic behaviour of both ground states in the transition region. Two mechanisms for the nature of the transition are discussed, a “spin-flip” mechanism being the physically more reasonable one. The assumption of a simple Boltzmann distribution (“spin equilibrium”) may be ruled out for the solid but could be encountered in solutions.