Effect of nonequilibrium solvation on chemical reaction rates. Variational transition-state-theory studies of the microsolvated reaction Cl sup minus (H sub 2 O) sub n + CH sub 3 Cl

Journal Article · Wed Apr 25 00:00:00 EDT 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00165a014· OSTI ID:6653634

Tucker, S C; Truhlar, D G ^[1]

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1. Univ. of Minnesota, Minneapolis (USA)

The authors present a potential energy surface for the microhydrated S{sub N}2 reaction of a chloride ion with methyl chloride in the presence of one or two water molecules. All degrees of freedom are included. The authors analyze the stationary points corresponding to reactant, ion-dipole complex, and transition state for the monohydrated and the dihydrated reactions, and they use generalized transition-state theory to evaluate the rate constants for these reactions. A noteworthy feature of the dynamics calculations is that vibrational zero point effects are included, as are effects of quantization on vibrational heat capacities and entropies, and water molecules are treated as nonrigid. The authors find that the rate constant at 300 K decreases from the gas-phase value of 3.5 {times} 10{sup {minus}14} cm{sup 3} molecule {sup {minus}1} s{sup {minus}1} to a value of 1.1 {times} 10{sup {minus}17} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} for the monohydrated reaction and to a value of 3.7 {times} 10{sup {minus}20} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} for the dihydrated reaction.

• OSTI ID: 6653634
• Journal Information: Journal of the American Chemical Society; (USA), Vol. 112:9; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CHLORIDES
CHEMICAL REACTION KINETICS
METHYL CHLORIDE
CALCULATION METHODS
DATA ANALYSIS
MATHEMATICAL MODELS
POTENTIAL ENERGY
SOLVENTS
CHLORINATED ALIPHATIC HYDROCARBONS
CHLORINE COMPOUNDS
ENERGY
HALIDES
HALOGEN COMPOUNDS
HALOGENATED ALIPHATIC HYDROCARBONS
KINETICS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
REACTION KINETICS
400201* - Chemical & Physicochemical Properties