Abstract
Two-photon polarization measurements are shown to provide an incorrect symmetry assignment for the first excited state of phenanthrene, both in solution and in the vapor phase. Published assignments from one-photon, single-crystal measurements indicate a totally symmetric state, while the assignment from two-photon measurements indicates an antisymmetric state. Possible reasons for the failure of the two-photon symmetry assignment are low-frequency vibronic overlap, and interference among the diagonal tensor elements. Experimental evidence points to interference as the origin of the discrepancy.
Get full access to this article
View all access options for this article.
References
1.
McClain
W. M.
, J. Chem. Phys. 55 , 2789 (1971 ).
2.
Monson
P. R.
and
McClain
W. M.
, J. Chem. Phys. 53 , 29 (1970 ).
3.
Wirth
M. J.
Koskelo
A. C.
, and
Mohler
C. E.
, J. Chem. Phys. 87 , 4395 (1983 ).
4.
McClure
D. S.
, J. Chem. Phys. 22 , 1256 (1954 ).
5.
Craig
D. P.
and
Gordon
R. D.
, Proc. Royal Soc. London 228 , 69 (1965 ).
6.
Hohlneicher
G.
and
Dick
B.
, J. Chem. Phys. 70 , 5427 (1979 ).
7.
Wirth
M. J.
Koskelo
A. C.
Mohler
C. E.
, and
Lentz
B. A.
, Anal. Chem. 53 , 2045 (1981 ).
8.
Mohler
Carol E.
, Ph.D. Thesis, University of Wisconsin-Madison (1985 ).
9.
Otokozawa
H.
Inomata
S.
Makami
N.
, and
Ito
M.
, Bull. Chem. Soc. Japan 50 , 2899 (1977 ).
10.
Hochstrasser
R. M.
and
Noe
L. J.
, Chem. Phys. Lett. 5 , 489 (1970 ).
11.
Craig
D. P.
Hollas
J. M.
Redies
M. F.
, and
Wait
S. C.
Jr.
, Phil. Trans. A253 , 543 (1961 ).
12.
Luther
H.
and
Operskalski
J.
, Naturwissenschaften 37 , 376 (1950 ).