Variational transition state theory. Three-year progress report

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

OSTI ID:10179385

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: USDOE, Washington, DC (United States)
• DOE Contract Number: FG02-86ER13579
• OSTI ID: 10179385
• 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
664300
74 ATOMIC AND MOLECULAR PHYSICS
ATOMS
CHEMICAL AND PHYSICOCHEMICAL PROPERTIES
CHEMICAL REACTION KINETICS
CHLORINE IONS
COLLISION PHENOMENA
COMPUTER CALCULATIONS
DEUTERIUM
DYNAMICS
FLUORINE
GASES
HYDROGEN
ISOTOPE EFFECTS
METHYL CHLORIDE
MOLECULE COLLISIONS
OXYGEN
P CODES
PARTITION FUNCTIONS
POTENTIAL ENERGY
PROGRESS REPORT
QUANTIZATION
QUANTUM MECHANICS
REACTION INTERMEDIATES
RESEARCH PROGRAMS
VARIATIONAL METHODS