Potential energy surfaces and reaction dynamics of polyatomic molecules

Technical Report · Fri Nov 01 04:00:00 EST 1991

DOI:https://doi.org/10.2172/5926228· OSTI ID:5926228

Chang, Yan-Tyng

A simple empirical valence bond (EVB) model approach is suggested for constructing global potential energy surfaces for reactions of polyatomic molecular systems. This approach produces smooth and continuous potential surfaces which can be directly utilized in a dynamical study. Two types of reactions are of special interest, the unimolecular dissociation and the unimolecular isomerization. For the first type, the molecular dissociation dynamics of formaldehyde on the ground electronic surface is investigated through classical trajectory calculations on EVB surfaces. The product state distributions and vector correlations obtained from this study suggest very similar behaviors seen in the experiments. The intramolecular hydrogen atom transfer in the formic acid dimer is an example of the isomerization reaction. High level ab initio quantum chemistry calculations are performed to obtain optimized equilibrium and transition state dimer geometries and also the harmonic frequencies.

• Research Organization: Lawrence Berkeley Lab., CA (United States)
• Sponsoring Organization: DOE; NSF; USDOE, Washington, DC (United States); National Science Foundation, Washington, DC (United States)
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 5926228
• Report Number(s): LBL-31622; ON: DE92008314
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALDEHYDES
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
DIMERS
DISSOCIATION
DYNAMICS
ELECTRONIC STRUCTURE
FORMALDEHYDE
FORMIC ACID
ISOMERIZATION
MECHANICS
MOLECULES
MONOCARBOXYLIC ACIDS
ORGANIC ACIDS
ORGANIC COMPOUNDS
POLYATOMIC MOLECULES
RAMAN SPECTRA
SPECTRA