Probing the transition state with negative ion photodetachment: The Cl + HCl and Br + HBr reactions

Journal Article · Thu Feb 22 04:00:00 EST 1990 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100367a034· OSTI ID:6664533

Metz, R B; Weaver, A; Bradforth, S E; Kitsopoulos, T N; Deumark, D M ^[1]

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1. Univ. of California, Berkeley (USA)

The transition-state region for neutral hydrogen-transfer reactions can be probed by photodetaching the appropriate stable, hydrogen-bonded negative ion. This paper presents a detailed account of this method, in which the Cl + HCl and Br + HBr reactions are investigated by photoelectron spectroscopy of ClHCl{sup {minus}}, BrHBr{sup {minus}}, and the corresponding deuterated species. The photoelectron spectra exhibit resolved vibrational structure attributed to the unstable neutral (ClHCl) or (BrHBr) complex. The BrHBr{sup {minus}} and BrDBr{sup {minus}} spectra exhibit narrow (15-20 meV) peaks that are likely to result from reactive resonance states supported by the Br + HBr potential energy surface, as well as peaks that appear to be from an electronically excited state of the (BrHBr) complex. The BrHBr{sup {minus}} and BrDBr{sup {minus}} results have been analyzed to yield an effective collinear potential energy surface for the Br + HBr reaction.

• OSTI ID: 6664533
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 94:4; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CALCULATION METHODS
DATA
DATA ANALYSIS
ELECTRON SPECTROSCOPY
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
HYDROBROMIC ACID
HYDROCHLORIC ACID
HYDROGEN COMPOUNDS
HYDROGEN TRANSFER
INFORMATION
INORGANIC ACIDS
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
PHOTOELECTRON SPECTROSCOPY
SPECTROSCOPY
VIBRATIONAL STATES