Energies of C[sub 2]H[sub 5]O and C[sub 2]H[sub 5]O[sup +] isomers

Journal Article · Wed Feb 22 00:00:00 EST 1995 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.468640· OSTI ID:6576721

Curtiss, L A ^[1]; Lucas, D J ^[2]; Pople, J A ^[3]

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1. Chemical Technology Division/Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States)
2. Physics Department, Northern Michigan University, Marquette, Michigan 49855 (United States)
3. Department of Chemistry, Northwestern University, Evanston, Illinois 60208 (United States)

The Gaussian-2 (G2) theoretical procedure, based on [ital ab] [ital initio] molecular orbital theory, is used to calculate the energies of C[sub 2]H[sub 5]O and C[sub 2]H[sub 5]O[sup +] isomers. The ethoxy radical cation (CH[sub 3]CH[sub 2]O[sup +]) is found to have a [sup 3][ital A][double prime] ground state while the singlet state is predicted to be unstable to rearrangement. The G2 adiabatic ionization potential of ethoxy radical is 10.32 eV in good agreement with a new ionization potential reported by Ruscic and Berkowitz of 10.29[plus minus]0.08 eV from photoionization studies. The 2-hydroxyethyl radical (CH[sub 2]CH[sub 2]OH) has three isomers of nearly equal energy (within 1.6 kcal/mol). No stable 2-hydroxyethyl cation was located as it collapses to either O-protonated oxirane or 1-hydroxyethyl cation. The G2 appearance potential of CH[sub 3]CHOH[sup +] from ethanol of 10.79 eV is in excellent agreement with the recent photoionization value of 10.801[plus minus]0.005 eV. The [alpha](C--H), [beta](C--H), and O--H bond dissociation energies of ethanol are 94.9, 101.9, and 104.6 kcal/mol, respectively. The G2 result for the O--H bond energy is in good agreement with experiment while the results for the other two bond energies suggest that the experimental values for these quantities may be low.

• Research Organization: Argonne National Laboratory (ANL), Argonne, IL
• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 6576721
• Journal Information: Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 102:8; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

664100* -- Theory of Electronic Structure of Atoms & Molecules-- (1992-)
74 ATOMIC AND MOLECULAR PHYSICS
ADIABATIC PROCESSES
ALCOHOLS
ALKOXY RADICALS
ALKYL RADICALS
ATMOSPHERIC CHEMISTRY
CATIONS
CHARGED PARTICLES
CHEMICAL REACTIONS
CHEMISTRY
COMBUSTION
CONTROL
DISSOCIATION
DISSOCIATION ENERGY
ENERGY
ENERGY LEVELS
ETHANOL
ETHOXY RADICALS
ETHYL RADICALS
GAUSSIAN PROCESSES
GROUND STATES
HYDROXY COMPOUNDS
IONIZATION POTENTIAL
IONS
ISOMERS
ORGANIC COMPOUNDS
OXIDATION
POLLUTION CONTROL
RADICALS
THERMOCHEMICAL PROCESSES