Crossed molecular beams study on the formation of vinylacetylene in Titan's atmosphere.

The reaction of ground-state ethynyl radicals, C(2)H(X(2)Sigma(+)), with d(4)-ethylene, C(2)D(4)(X(1)A(g)), was investigated at a collision energy of 20.6 +/- 0.4 kJ mol(-1) utilizing the crossed-beams technique.

The Bis(pentafluoroethyl)phosphinous acid (C2F5)2POH.

The industrial product (C(2)F(5))(3)PF(2) is transformed into the phosphinic acid chloride (C(2)F(5))(2)P(O)Cl, which reacts with an excess of Bu(3)SnH in a clean, multistep reaction to give the stannyl derivative (C(2)F(5))(2)POSnBu(3). Subsequent treatment with gaseous HBr leads to the formation of (C(2)F(5))(2)POH, which is isolated in 70 % yield. Besides (CF(3))(2)POH, bis(pentafluoroethyl)phosphinous acid, (C(2)F(5))(2)POH, represents the second known example of a phosphinous acid that is predicted by using density functional theory calculations at the B3PW91/6-311G(3d,p) level to be more stable than the phosphane oxide tautomer, the energy difference being 11.

A crossed molecular beam study on the synthesis of the interstellar 2,4-pentadiynylidyne radical (HCCCCC).

Crossed molecular beam experiments are performed to elucidate the synthesis of the 2,4-penta-diynylidyne [HCCCCC(X (2)Pi)] radical under single collision conditions--a crucial reaction intermediate to form polycyclic aromatic hydrocarbons and carbonaceous nanostructures in the interstellar medium and in combustion flames. The experiments demonstrate that the chemical dynamics of ground state carbon reacting with diacetylene [HCCCCH(X (1)Sigma(g)(+))] are indirect and proceed via addition of the electrophilic carbon atom to the pi electron density of the diacetylene molecule yielding ultimately the carbenelike HCCCCCH(X (3)Sigma(g)(-)) molecule. This intermediate fragments via hydrogen atom emission to yield the 2,4-pentadiynylidyne [HCCCCC(X (2)Pi)] radical.

Infrared spectrum of matrix isolated selenoformaldehyde, CH2Se, and CD2Se.

Thermolysis of highly diluted (CH2Se)3 or (CD2Se)3 in a flow of argon with subsequent quenching of the products in an matrix at 15 K yields monomeric CH2Se and CD2Se, respectively. Six fundamental vibrations upsilon1 = 2972.5, upsilon2 = 1413.

Organic glass-forming materials: 1,3,5-tris(naphthyl)benzene derivatives.

The organic glass-forming materials 1,3-bis(1-naphthyl)-5-(2-naphthyl)benzene (2) and its partially deuterated analogue, 1,3-bis(1-naphthyl-d(7))-5-(2-naphthyl)benzene (2-d(14)), have been synthesized on a gram scale using Suzuki coupling reactions. Detailed spectroscopic studies afford complete NMR assignments (1H, 2H, 13C) for both compounds. Modest energy barriers for the interconversion of atropisomers (ca.

Ring opening of 2,5-didehydrothiophene: matrix photochemistry of C4H2S isomers.

Irradiation (lambda > 254 nm) of matrix-isolated 2,5-diiodothiophene (10) gives rise to IR bands assigned to ethynylthioketene (6). Diethynyl sulfide (3), which would form in the process of retro-Bergman cyclization of the incipient 2,5-didehydrothiophene (4), is not detected. Under the same irradiation conditions, matrix-isolated diethynyl sulfide (3) rearranges to thioketene 6 and butatrienethione (5), the global minimum on C4H2S potential energy surface.

Organic glasses with exceptional thermodynamic and kinetic stability.

Vapor deposition has been used to create glassy materials with extraordinary thermodynamic and kinetic stability and high density. For glasses prepared from indomethacin or 1,3-bis-(1-naphthyl)-5-(2-naphthyl)benzene, stability is optimized when deposition occurs on substrates at a temperature of 50 K below the conventional glass transition temperature. We attribute the substantial improvement in thermodynamic and kinetic properties to enhanced mobility within a few nanometers of the glass surface during deposition.

Neutron reflectivity measurements of the translational motion of tris(naphthylbenzene) at the glass transition temperature.

The translational dynamics of the low molecular weight glass-former tris(naphthylbenzene) have been studied on the length scale of a few nanometers at the glass transition temperature Tg. Neutron reflectivity was used to measure isotopic interdiffusion of multilayer samples created by physical vapor deposition. Deposition with the substrate held at Tg-6 K allows observation of dynamics characterizing the equilibrium supercooled liquid.

Ring opening of 2,5-didehydrothiophene: structures and rearrangements of C4H2S isomers.

Electronic structures and rearrangement pathways of several C4H2S isomers are computationally investigated by methods based on coupled cluster theory and density functional theory. Six singlet C4H2S isomers lie within ca. 30 kcal/mol above butatrienethione (6), the apparent global minimum.

Access to the naphthylcarbene rearrangement manifold via isomeric benzodiazocycloheptatrienes.

Irradiation (lambda = 670 or >613 nm) of 4,5-benzodiazocycloheptatriene (15), matrix isolated in argon at 10 K, produces primarily 2,3-benzobicyclo[4.1.0]hepta-2,4,6-triene (9) accompanied by small amounts of triplet 4,5-benzocycloheptatrienylidene (2) and 2-naphthylcarbene (10).