Is the oxywater radical cation more stable than neutral oxywater?

Journal Article · Wed May 01 04:00:00 EDT 1996 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.471470· OSTI ID:283806

Xie, Y; Allen, W D; Yamaguchi, Y; Schaefer, III, H F ^[1]

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1. Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602 (United States)

{ital Ab} {ital initio} quantum mechanical methods have been applied to the distonic oxywater (H{sub 2}OO{sup +}) and conventional hydrogen peroxide (HOOH{sup +}) cations. The investigation employed basis sets up to triple-{zeta} plus double polarization plus {ital f} functions (TZ2Pf) and levels of correlation up to coupled-cluster including single, double, and perturbatively treated connected triple excitations [CCSD(T)]. The HOOH{sup +} cation, which is planar, has both {ital trans} ({ital C}{sub 2{ital h}}) and {ital cis} ({ital C}{sub 2{ital v}}) conformations, the former predicted to be 8 kcalmol{sup {minus}1} lower in energy. At the highest level of theory, the distonic H{sub 2}OO{sup +} structure is found to lie 23 kcalmol{sup {minus}1} above the conventional {ital trans} form. The barrier separating the oxywater cation from HOOH{sup +} is about 33 kcalmol{sup {minus}1}, roughly ten times larger than that for the neutral oxywater species. Accordingly, ionization greatly enhances the stability of the nonconventional oxywater structure. Harmonic vibrational frequencies and their infrared intensities are also reported for the H{sub 2}O{sup +}{sub 2} species. Symmetry breaking of Hartree{endash}Fock electronic wave functions is found in HOOH{sup +}, which adversely affects certain vibrational frequencies due to nearby singularities in related quadratic force constants. This problem is efficaciously overcome via Brueckner methods [BD and BD(T)].

• DOE Contract Number: FG05-94ER14428
• OSTI ID: 283806
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 19 Vol. 104; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

66 PHYSICS
AB INITIO CALCULATIONS
ELECTRONIC STRUCTURE
FORCE CONSTANTS
HYDROGEN PEROXIDE
INFRARED SPECTRA
LINE INTENSITY
RADICALS
VIBRATIONAL STATES
WATER
WAVE FUNCTIONS