The electronic structures and spectra of nitrite ion, nitrosomethane, nitrosamine, and nitrate ion have been calculated by a semiempirical method, which includes both the π‐electron system and, in a more limited manner, the σ‐electron system. The calculated transition energies and intensities for the first three compounds above agree fairly satisfactorily with experiment. For nitrate ion, however, it seems possible that the lowest observed transition may be a very low energy n→σ* transition, σ* being an antibonding σ orbital, rather than one of the n→π* transitions considered in the present work.
REFERENCES
1.
2.
3.
4.
5.
T.
Anno
and A.
Sadô
, J. Chem. Phys.
29
, 1170
(1958
)., J. Chem. Phys.
6.
7.
8.
9.
Recently
Parks
and Parr
have applied this method to the formaldehyde molecule. [J. Chem. Phys.
32
, 1657
(1960
).]10.
11.
12.
C. C. J. Roothaan, Two‐Center Coulomb Integrals (Special Technical Report of the Laboratory of Molecular Structure and Spectra, University of Chicago, Chicago, Illinois, 1955);
13.
G. W. Wheland, Resonance in Organic Chemistry (John Wiley & Sons, Inc., New York, 1955).
14.
R. S.
Mulliken
, C. A.
Reike
, D.
Orloff
, and H.
Orloff
, J. Chem. Phys.
17
, 1248
(1949
).15.
16.
H. A.
Skinner
and H. O.
Pritchard
, Trans. Faraday Soc.
49
, 1254
(1953
);17.
18.
C. E. Moore, Natl. Bur. Standards (U.S.) Circ. 467 (1949).
19.
20.
L. E. Orgel, J. Chem. Soc. 1953, 1276.
21.
J. A. Friend and L. E. Lyons, J. Chem. Soc. 1959, 1572.
This content is only available via PDF.
© 1961 American Institute of Physics.
1961
American Institute of Physics
You do not currently have access to this content.