Direct calculation of equilibrium constants for isotopic exchange reactions by ab initio molecular orbital theory

Journal Article · Wed Apr 23 04:00:00 EST 1980 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00529a090· OSTI ID:7142005

Hout, Jr, R F; Wolfsberg, M; Hehre, W J

The ability of simple levels of ab initio molecular orbital theory to describe with reasonable accuracy the energetics of isotopic exchange processes is demonstrated. Three levels of ab initio molecular orbital theory have been surveyed. The first two levels are single-determinant Hartree-Foch methods utilizing the 3-21G split-valence and 6-31G* polarization basis sets. The third level, which is computationally the most complex, uses the 6-31G* basis set but allows for partial account of electron correlation by way of Moller-Plesset perturbation theory terminated at second order. Theoretical and spectroscopic equilibrium constants for reactions XH + XD reversible XD + H/sub 2/ where XD is a hydride of the first row of the periodic table are tabulated. (BLM)

• Research Organization: Univ. of California, Irvine
• DOE Contract Number: AT03-76ER70188
• OSTI ID: 7142005
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 102:9; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
400302 -- Organic Chemistry-- Isotope Effects-- (-1987)
DATA
DATA COMPILATION
DEUTERIUM
HYDRIDES
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
ISOTOPIC EXCHANGE
KINETICS
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
REACTION KINETICS
STABLE ISOTOPES
TABLES