Journal ArticleDOI
The unimolecular triple dissociation of glyoxal: transition-state structures optimized by configuration interaction and coupled cluster methods
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TLDR
In this article, the triple whammy mechanism for the unimolecular dissociation of glyoxal was investigated and it was shown unambiguously that the triple dissociation mechanism is operative under conditions used in the laboratory to investigate the photochemistry.Abstract:
Several high-level ab initio theoretical methods have been used to investigate the proposed (1980) triple whammy mechanism for the unimolecular dissociation of glyoxal. Basis sets of double zeta plus polarization (DZ + P) and triple zeta plus double polarization (TZ + 2P) quality have been used in connection with CISD, CCSD, and CCSDT-1 theoretical methods. The theoretical studies show unambiguously that the triple dissociation mechanism is operative under conditions used in the laboratory to investigate glyoxal photochemistry. Also confirmed, contrary to existing experiments, is the early (1975) theoretical prediction of Dykstra that the C-C single bond distance of cis-glyoxal is longer than for trans-glyoxal. Vibrational frequencies for both cis- and trans-glyoxal are predicted and show good qualitative agreement with existing experimental data.read more
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Mechanism of CO2 Reduction at Copper Surfaces: Pathways to C2 Products
TL;DR: In this article, the reduction of CO2 to C2 products on copper electrodes has been investigated using density functional theory simulations and experimental observations. But, the results of the experiments were limited to the (100 and 111) facets of copper.
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Ab initio molecular dynamics: Propagating the density matrix with Gaussian orbitals. III. Comparison with Born–Oppenheimer dynamics
H. Bernhard Schlegel,Srinivasan S. Iyengar,Xiaosong Li,John M. Millam,Gregory A. Voth,Gustavo E. Scuseria,Michael J. Frisch +6 more
TL;DR: In this article, an extended Lagrangian is used to propagate the density matrix in a basis of atom centered Gaussian functions, and the results of trajectory calculations obtained by this method are compared with the Born-Oppenheimer approach (BO), in which the density is converged at each step rather than propagated.
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UV photodissociation of oxalyl chloride yields four fragments from one photon absorption
TL;DR: In this paper, the photodissociation of oxalyl chloride, (ClCO)2, has been studied near 235 nm using the photofragment imaging technique, yielding state-resolved angular and translational energy distributions.
Journal ArticleDOI
An experimental potential energy surface for internal rotation in glyoxal
TL;DR: The torsional potential energy surface (TPES) for internal rotation of the CHO group in glyoxal CHOCHO has been derived experimentally by fitting observed energies for the torsion vibration ν7 in both trans and cis-glyoxal to those calculated with the hindered rotation formalism of Lewis, Malloy, Chao, and Laane as mentioned in this paper.
Journal ArticleDOI
Formyl fluoride photodissociation: Potential energy surface features of singlet HFCO
TL;DR: In this article, the unimolecular dissociation of formyl fluoride to hydrogen fluoride and carbon monoxide has been examined theoretically and a barrier height of ∼47 kcal/mol−1 to the molecular dissociation has been predicted.