A classical trajectory study of intramolecular energy redistribution and overtone-induced dissociation in dimethyl peroxide

Journal Article · Thu May 30 04:00:00 EDT 1991 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100164a010· OSTI ID:5975877

Budenholzer, F E; Chen, C; Huang, C M; Leong, K C ^[1]

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1. Fu Jen Catholic Univ., Hsinchuang (Taiwan)

The classical trajectory method has been used to model intramolecular energy redistribution (IVR) and overtone-induced dissociation of CH{sub 3}OOCH{sub 3} and its deuterium analogue. Trajectories were run over three potential energy surfaces: (1) a basic surface in which all stretches and bends (except the O-O stretch which was described as a Morse oscillator) were described as pure harmonic oscillators, (2) the basic surface with the addition of quadratic cross terms, and (3) the basic surface with all CH(D) stretches replaced by Morse oscillators. Three types of trajectories were calculated: (1) long time trajectories of up to 40 ps to determine the dissociation lifetime and dynamics, (2) short time trajectories of 2 ps, used to probe the IVR dynamics, and (3) ensembles of 0.1-ps trajectories, used to determine the rates of energy decay from the initially excited CH(D) bonds. In general, energy flows irreversibly from the initially excited CH bond on the order of 0.1 ps and quickly disperses throughout the molecule. Dissociation occurred in less than 40 ps only when the total initial energy was at least 48 kcal/mol above the zero-point energy.

• OSTI ID: 5975877
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 95:11; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACTIVATION ENERGY
BENDING
DATA
DEFORMATION
DISSOCIATION
ENERGY
ENERGY LEVELS
ENERGY TRANSFER
EXCITED STATES
INFORMATION
ISOTOPE EFFECTS
MATHEMATICAL MODELS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OSCILLATION MODES
OXYGEN COMPOUNDS
PEROXIDES
POTENTIAL ENERGY
THEORETICAL DATA
TIME DEPENDENCE