Variational transition state theory

Technical Report · Fri Dec 20 04:00:00 EST 1991

OSTI ID:7252830

Truhlar, D G

This project is concerned with the development and use of variational transition state theory to calculate reaction rates of gas-phase chemical reactions. Potential energy surfaces were modeled for specific reactions such as Cl + H{sub 2}, HCl + H, Cl{sup {minus}} + CH{sub 3}*Cl, Cl{sup {minus}}(H{sub 2}O) + CH{sub 3}*Cl, and F + H{sub 2}. New methods for interfacing electronic structure theory with dynamics were worked on; semiempirical molecular orbital theory is used to carry out direct dynamics calculations. Interpolated variational transition state theory is also used to carry out dynamics calculations without fitting a global potential energy surface. New theoretical approximations are under study, such as large-curvature tunneling including excited states, correlation of quantized transition state structure , optimization of stationary points on potential energy surfaces, calculation of quantal partition functions for hindered internal rotators, mode-mode coupling in quantum partition functions, and definition of reaction-path coordinates. Kinetic isotope effects are studied. Several enhancements have been made to the POLYRATE code. 1 tab. (DLC)

• Research Organization: Minnesota Univ., Minneapolis, MN (United States). Dept. of Chemistry
• Sponsoring Organization: DOE; USDOE, Washington, DC (United States)
• DOE Contract Number: FG02-86ER13579
• OSTI ID: 7252830
• Report Number(s): DOE/ER/13579-6; ON: DE92040498
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
664300 -- Atomic & Molecular Physics-- Collision Phenomena-- (1992-)
74 ATOMIC AND MOLECULAR PHYSICS
ATOMS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHLORINATED ALIPHATIC HYDROCARBONS
CHLORINE IONS
COLLISIONS
COMPUTER CALCULATIONS
COMPUTER CODES
DEUTERIUM
DOCUMENT TYPES
DYNAMICS
ELEMENTS
ENERGY
FLUIDS
FLUORINE
FUNCTIONS
GASES
HALOGENATED ALIPHATIC HYDROCARBONS
HALOGENS
HYDROGEN
HYDROGEN ISOTOPES
IONS
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
MECHANICS
METHYL CHLORIDE
MOLECULE COLLISIONS
NONMETALS
NUCLEI
ODD-ODD NUCLEI
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
OXYGEN
P CODES
PARTITION FUNCTIONS
POTENTIAL ENERGY
PROGRESS REPORT
QUANTIZATION
QUANTUM MECHANICS
REACTION INTERMEDIATES
REACTION KINETICS
RESEARCH PROGRAMS
STABLE ISOTOPES
VARIATIONAL METHODS