Analysis of the laser photoelectron spectrum of CH/sup -//sub 2/

Journal Article · Fri Nov 15 04:00:00 EST 1985 · J. Chem. Phys.; (United States)

OSTI ID:5239773

Bunker, P R; Sears, T J

We have simulated the photoelectron spectrum of CH/sup -//sub 2/ using the model described previously (Sears and Bunker, J. Chem. Phys. 79, 5265 (1983)). The optimization of the fit of the simulated spectrum to the recently observed spectrum of Lineberger and co-workers (J. Chem. Phys. 81, 1048 (1984) and preceding paper) has enabled us to determine the rotation-bending energy levels of triplet CH/sub 2/ over an energy range of more than 1 eV. It has also enabled us to determine that the rotational temperature of the CH/sup -//sub 2/ in the experiment is 220 K and that, for v/sub 2/ = 1, the vibrational temperature is 680 K. For CH/sup -//sub 2/ we determine that a/sub e/ = 103/sup 0/ and that ..nu../sub 2/ = 1230 cm/sup -1/. The singlet--triplet splitting in methylene is determined to be 3150 +- 30 cm/sup -1/ (0.3905 +- 0.004 eV, 9.01 +- 0.09 kcal/mol) from the photoelectron spectrum, in excellent agreement with the more accurate value previously obtained from LMR spectroscopy (McKellar et al., J. Chem. Phys. 79, 5251 (1983)) of 3165 +- 20 cm/sup -1/ (0.3924 +- 0.0025 eV, 9.05 +- 0.06 kcal/mol), and the electron affinity of triplet CH/sub 2/ is determined to be 0.652 +- 0.006 eV.

• Research Organization: Herzberg Institute of Astrophysics, National Research Council of Canada, Ottawa, Ontario, Canada K1A 0R6
• OSTI ID: 5239773
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 83:10; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
AFFINITY
ANIONS
CHARGED PARTICLES
ELECTRON SPECTROSCOPY
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXCITED STATES
IONS
METHYLENE RADICALS
MOLECULAR STRUCTURE
PHOTOELECTRON SPECTROSCOPY
RADICALS
ROTATIONAL STATES
SPECTROSCOPY
VIBRATIONAL STATES