High resolution infrared absorption spectra of BCl/sub 3/ and BCl/sub 2/F dissolved in solid argon and solid krypton
High-resolution (approx. =0.035 cm/sup -1/) infrared absorption spectra of BCl/sub 3/ and BCl/sub 2/F dissolved in solid argon and krypton have been obtained. The solids were grown from liquid solutions, were 1.4 cm thick, and were reasonably clear optically. The ..nu../sub 2/, ..nu../sub 3/, ..nu../sub 1/+..nu../sub 4/, ..nu../sub 3/+..nu../sub 4/, ..nu../sub 1/ +..nu../sub 3/, and 2..nu../sub 3/ bands of BCl/sub 3/ were found, and the positions of the ..nu../sub 1/ and ..nu../sub 4/ bands of BCl/sub 2/F were inferred. An observed perturbation of the ..nu../sub 2/ band of /sup 10/BCl/sub 3/ is explained by invoking a lattice-induced distortion of BCl/sub 3/ from planarity. The observed spectral lines are very narrow, so the absorption bands of different boron and chlorine isotopomers are well resolved. The observed full spectral width of the absorption lines at half maximum absorbance is <0.04 cm/sup -1/ for the ..nu../sub 2/ lines of BCl/sub 3/ and approx.0.08 cm/sup -1/ for the other fundamentals. The wave number nu-tilde of a given line depends on solid solvent and on temperature T; dnu-tilde/dT is within the range 0.014< or =dnu-tilde < or =0.09 cm/sup -1///sup 0/C for all bands. Anharmonicities and harmonic frequencies have been obtained from the data, and the anharmonicity constants lie between -1.8 and 0.8 cm/sup -1/. Energies have been estimated for the first excited states of the ..nu../sub 1/ and ..nu../sub 4/ modes of BCl/sub 3/ and also for the A'/sub 1/ and A'/sub 2/ levels of the v/sub 3/=v/sub 4/=1 state of BCl/sub 3/. The usual theory of harmonic oscillators having D/sub 3h/ symmetry does not adequately describe the ..nu../sub 3/ and ..nu../sub 4/ band positions and isotopic splittings.
- Research Organization:
- University of California, Los Alamos Scientific Laboratory, Los Alamos, New Mexico 87545
- OSTI ID:
- 5429082
- Journal Information:
- J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 72:12; ISSN JCPSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
Molecular & Chemical Physics
74 ATOMIC AND MOLECULAR PHYSICS
ABSORPTION SPECTRA
ARGON
BORON CHLORIDES
BORON COMPOUNDS
BORON FLUORIDES
CHLORIDES
CHLORINE COMPOUNDS
ELEMENTS
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
INFRARED SPECTRA
KRYPTON
LINE WIDTHS
NONMETALS
RARE GASES
RESOLUTION
SOLIDS
SPECTRA