A variational quantum mechanical protocol is presented for the computation of rovibrational energy levels of semirigid molecules using discrete variable representation of the Eckart-Watson Hamiltonian, a complete, "exact" inclusion of the potential energy surface, and selection of a vibrational subspace. Molecular symmetry is exploited via a symmetry-adapted Lanczos algorithm. Besides symmetry ...

These experiments study the preparation of and product channels resulting from OCH(2)CHCH(2), a key radical intermediate in the O+allyl bimolecular reaction. The data include velocity map imaging and molecular beam scattering results to probe the photolytic generation of the radical intermediate and the subsequent pathways by which the radicals access the energetically allowed product channels ...

Monomers of phenol and its ring-perdeuterated isotopologue phenol-d(5) were isolated in argon matrices at 15 K. The infrared (IR) spectra of these species were recorded and analyzed. In situ photochemical transformations of phenol and phenol-d(5) were induced by tunable UV laser light. The photoproducts have been characterized by IR spectroscopy supported by theoretical calculations of the infr...

CBS-QB3 calculations have been used to determine thermochemical and kinetic parameters of the isomerisation and decomposition reactions of the acetonylperoxy radical, CH3C(O)CH2OO* , which has been formed via the reaction of acetonyl radical with O2 leading to the formation of an energised peroxy adduct with a calculated well depth of near 111 kJ mol(-1). This species can undergo subsequent 1,5...

The photoisomerization dynamics of N-methyl-2-pyridone (NMP) dissolved in CH3CN have been interrogated by time-resolved electronic and vibrational absorption spectroscopy. Irradiation at two different wavelengths (330 or 267 nm) prepares NMP(S1) molecules with very different levels of vibrational excitation, which rapidly relax to low vibrational levels of the S1 state. Internal conversion with...

Reactions of unsaturated hydrocarbons with fluoroformyl cation (CFO+) and of ketene and diketene with CFO+ and CF3 have been studied in a Flowing Afterglow-Selected Ion Flow Tube (FA-SIFT) in helium at room temperature. Net F+ transfer from CFO+ to the neutral reactants, which is observed in the majority of cases studied, can be explained in terms of formation of a covalent adduct followed by e...

Dipivaloylketene (2) is obtained by flash vacuum pyrolysis of furan-2,3-dione 6 and dimerizes to 1,3-dioxin-4-one 3, which is a stable but reactive ketene. The transannular addition and rearrangement of enols formed by the addition of nucleophiles to the ketene function in 3 generates axially chiral 2,6,9-trioxabicyclo[3.3.1]nonadienes (bisdioxines) 4. When arylamines are used as the nucleophil...