Isomerization of 1,2-diiodoethylene in a laser-induced chemical reaction of I2 + C2H2

A laser-induced chemical reaction of I₂ + C₂H₂ has been studied and the formation of cis and tians isomers of 1,2-diiodoethylene has been observed. The ratio of the two isomers of 1,2-diodoethylene changes markedly upon changing the laser wavelengths of excitation of the I₂ molecule     

Resonant cars spectroscopy of s-tetrazine vapour

CARS experiments on s-tetrazine vapour show that the electronic resonance enhancement in the Q-branch is most effective for the lower J values. This suggests that the radiationless relaxation rate in the excited state increases with rotational quantum number. Delayed picosecond CARS experiments indicate that the rotation-vibration coupling for the 1008 cm^?1 ground-state vibrational mode is approximately 2 MHz.     

A new approach to the measurement of the momentum densities in solids using an electron microscope

A new approach to the direct determination of electron momentum distributions in solids, using a combination of electron microscopy and electron spectroscopy, is described. The technique is several orders of magnitude more sensitive than currently available ones. The results of measurements on amorphous carbon are presented and used to demonstrate the potential of this new technique.     

Effects of geometric distortions and substituents on rates of intersystem crossing; diazomethane and pyrazoline

We report a qualititive perturbation-theoretic analysis of the effects of substituents on the spin-orbit coupling and on the density of states in diazomethane and pyrazoline systems. The importance of the form of the distortion which accompanies approach to the singlet-triplet crossing zone is also discussed with the aim of determining when reactions involving a spin multiplicity change can compete in rate with spin-conserving reactions.     

Effect of collision and magnetic field on quantum beat in biacetyl

Molecular quantum beats are shown for the case of biacetyl, to vary strongly under the influence of weak magnetic fields. Values for dephasing constants for a gas-phase molecular system were determined. Information on sub-Doppler level splittings in the intersystem-crossing process is obtained.     

Picosecond rotational diffusion by differential single-photon fluorescence spectroscopy

The rotational diffusion contants of rhodamine-6G, coumarin-1 and N-acetyltryptophanamide in various solvents have been determined by an experimental method where the vertically and horizontally polarized fluorescence spectra are measured simultaneously by the same detector. The results indicate that the Debye—Stokes—Einstein model does not hold for coumarin-1 and N-acetyltryptophanamide in ethylene glycol.     

Electronic absorption spectroscopy of cooled supersonic expansions: dynamics of the 1B1u state of trans-butadiene

An ultraviolet absorption technique is developed for studying molecules cooled in a supersonic expansion. In this experiment, the temperature-dependent contribution to the diffuseness of electronically excited states is reduced for CS₂ and butadiene. The broadness of the spectral features of the butadiene ¹B_1u state is independent of temperature     

Ab initio calculations of the equilibrium geometry of cis and trans methylglyoxal using the force method

Ab initio calculations of the equilibrium ground-state conformation of trans-methylglyoxal, CH₃COCHO, have been carried out using the gradient method and a 4-3 IG basis set. The results are compared with experiment and with a theoretical geometry computed using an STO-3G basis set, and the more usual stepwise optimization of the parameters. The molecular orbital energies, dipole moment and ionization energy are calulated. Calculations are also carried out on the cis-isomer and the barrier to cis-trans isomerization is obtained.     

EPR study of oriented photoexcited triplets of porphyrins and chlorophylls in a liquid crystal

An EPR study of the photoexcited triplet state of porphyrins, Chl a and the covalently linked dimer of Zn pyrochlorophyllide a, in a liquid crystal, is reported The metalloporphyrins interact to form excimers The low intramolecular energy transfer rate in the dimer (? 10⁶s^?1) suggests that the unfolded form predominates.     

Effect of quadratic interactions on the resonance raman scattering of T × t2 jahn-teller systems

Raman excitation profiles and depolarization dispersion curves are calculated for T × t₂ Jahn-Teller systems that are subject to quadratic vibronic (Renner-Teller) coupling as well as frequency changes of the active vibrational mode.     

The zero point average structure of isobutane as determined by electron diffraction and microwave spectroscopy

The molecular structure of isobutane in the gas phase was investigated by combining electron diffraction data with microwave spectroscopic rotational constants of Lide.The analysis indicated that the tertiary C-H distance (r_g = 1.122±0.006 Å) was substantially longer than the average methyl C-H distance (r_g = 1.113±0.002 Å). Other structural parameters obtained were: r_g(C-C) = 1.535±0.001 Å, ∠CCC = 110.8±0.2°, and the average ∠CCH (methyl) = 111.4±0.2°.     

Thermal properties of xenon adsorbed on graphite

We report theoretical results for dynamical and thermodynamic properties of the bare graphite (0001) surface, and with a physisorbed monolayer of xenon. The surface vibrations of graphite are less pronounced than those in more isotropic crystals. The surface-excess specific heat of the bare surface peaks at 45 K, that of the xenon at 13.5 K.     

CNDO/2 calculations of rotational barriers in N.N-dimethylamino-azines: Lineshape study of the barrier in 3-dimethylamino-1,2,4-triazine

3-Dimethylamino-1,2,4-triazine has been prepared and the hindered rotation around the exocyclic C-N bond has been studied by a complete lineshape method. CNDO/2 calculations on dimethylamino derivatives of pyridine, pyrimidine, 1,2,4-triazine and 1,3,5-triazine have been performed, and it is found that the calculations satisfactorily reproduce the experimental data. The barrier heights are also discussed in terms of total and π-charge densities obtained from CNDO/2 calculations.     

On the planarity and resonance effect of tetraphenylporphyren and its metallocomplexes

Based on Lennard-Jones potential and resonance effect calculations it has been demonstrated that in solution tetraphenylporphyrin assumes a structure closer to coplanar by 17° from that in the solid state. In the case of metalloporphyrin the tendency towards coplanarity is even greater, about 40°. The minimum in the energy curve is of the same order of magnitude as reported values of free energy of activation for the phenyl rotation.     

Spectroscopy of large molecules in inert gas clusters

Aromatic hydrocarbons provide nucleation centers for the formation of clusters of inert gases in high-flow supersonic beams. Large clusters of Ar, each containing a single tetracene (T) molecule, were prepared by supersonic expansion of the seeded gas at pressures p = 3000–13000 Torr and interrogated by laser-induced fluorescence spectroscopy Evidence is reported for homogeneous line broadening of large TAr_n clusters prepared at p? 8000 Torr.     

Crystalline hydrogen bonded adducts of oxygen bases with peroxybenzoic acids

The preparation and isolation of several crystalline 1 : 1 adducts of substituted peroxybenzoic acids with triphenylphosphine oxide, triphenylarsine oxide, and pyridine oxides, is reported. Infrared spectra indicate the presence of strong intermolecular hydrogen bonds in these adducts.     

The coulometric titration of bromate with cuprous copper

A coulometric procedure has been developed by which 18 to 240 μg quantities of bromate may be determined to within 0.3 μg. The bromate is allowed to react with bromide in an acid solution and electrolytically generated cuprous copper is used for the titration. A dual platinum electrode indicator system is used in an amperometric end-point procedure     

Excitation profiles of resonance raman spectra in condensed media

A simple model, obtained by reducing a multimode system to a simple coordinate, is proposed to explain the broadening of RRS in liquid or solid media. It is shown that the coherent excitation of the near continuous background of low-frequency modes can cause homogeneous broadening of RRS profiles. The model is applied to the excitation profile of β-carotene.     

The molecular structure of gaseous tetrachloro-p-benzoquinone and tetrachloro-o-benzoquinone by electron diffraction

The structures of tetrachloro-p-benzoquinone and tetrachloro-o-benzoquinone (p- and o-chloranil) have been investigated by gas electron diffraction. The ring distances are slightly larger and the carbonyl bonds slightly smaller than in the corresponding unsubstituted quinones. The molecules are planar to within experimental error, but small deviations from planarity such as those found for the para compound in the crystal are completely compatible with the data. Values for the geometrical parameters (r_a distances and bond angles) and for some of the more important amplitudes (l) with parenthesized uncertainties of 2σ including estimated systematic error and correlation effects are as follows. Tetrachloro-p-benzoquinone: D_2h symmetry (assumed); r(CO) = 1.216 Å(4), r(CC) = 1.353 Å(6), r(C-C) = 1.492 Å(3), r(C-Cl) = 1.701 Å(3), ∠C-C-C = 117.1° (7), ∠CC-C1 = 122.7° (2), l(CO)= 0.037 Å(5), l(CC) = l(C-C) - 0.008 Å(assumed) = 0.049 Å(7), and l(C-Cl) = 0.054 Å(3). Tetrachloro-o-benzoquinone: C_2v symmetry (assumed); r(CO) = 1.205 Å(5), r(CC) = 1.354 Å(9), r(C_cl-C_cl) = 1.478 Å(28), r(Co-C_cl) = 1.483 Å(24), r(C_o-C_o) = 1.526 Å(2), r(C-Cl)= 1.705 Å(3), <C_o-CO = 121.0° (22), ∠C-C-C = 117.2° (9), ∠C_co, ClC-Cl = 118.9° (22), ∠C_ccl, ClC-Cl = 122.2°(12), l(CO) = 0.039 Å(5), and l(C_cl-C_cl) = l(C_o-C_cl) = l( Co-Co) = l(CC) + 0.060 Å(equalities assumed) = 0.055 Å(9). Vibrational'shortenings (shrinkages) of a few of the long non-bond distances have also been measured.