Monopoles for pp* Transitions and Ground State in the Tyr Side Chaina


ATOM
Lb 
La 
Bb 
Ba 
G. S.
Cg
0.0
-1.6882
0.0
-0.5912
-0.1723
Cd1
-0.0922
1.0455
-1.0111
-1.4391
0.0359
Cd2
0.0922
1.0455
1.0111
-1.4391
0.0359
Ce1
-0.5251
-1.3250
-1.4370
1.1488
-0.3162
Ce2
0.5251
-1.3250
1.4370
1.1488
-0.3162
Cz
0.0
1.6172
0.0
0.7685
0.1415
Oh
0.0
0.6301
0.0
0.4033
0.6009
ATOM
Lb -La 
Lb -Bb
Lb -Ba
La -Bb
La -Ba
Ba -Bb
Cg
0.0
-2.4043
0.0
0.0
0.2603
0.0
Cd1
-0.3843
1.6473
-0.9905
-0.2764
0.1638
0.4128
Cd2
0.3843
1.6473
0.9905
0.2764
0.1638
-0.4128
Ce1
0.4684
1.2723
1.4209
-0.4330
-0.2623
-0.0475
Ce2
-0.4684
1.2723
-1.4209
0.4330
-0.2623
0.0475
Cz
0.0
-2.2793
0.0
0.0
0.6079
0.0
Oh
0.0
-1.1556
0.0
0.0
-0.6713
0.0

a Monopole positions are at the atomic centers. The monopole charges given here are in units of 10-10 esu. The monopole charges were calculated from a PPP calculation on phenol using the Nishimoto-Forster variable-b parameters (K. Nishimoto and L. S. Forster, Theor. Chim. Acta 3, 407-417 (1965); 4, 155-165 (1966)).


Transition Parameters for pp* Transitions in the Tyr Side Chaina


 
Transition
E (eV)
Ñx (A-1)
Ñy (A-1)
(r x Ñ)z (BM)
Bandwidth (nm)
Lb
4.4599
0.0
-0.1306
0.2103
12.4
La
5.3907
0.3574
0.0
0.0
9.4
Bb
6.5255
0.0
-0.7921
0.3544
7.1
Ba
6.5255
0.8884
0.0
0.0
7.1
 
a Because of the plane of symmetry, the z-component of the Ñ matrix element and the x, y components of the (r x Ñ) matrix element are zero. The two-fold axis of the phenol ring is the x-axis, positive toward the Oh atom. The y-axis is perpendicular to this and in-plane with the positive direction running from Cd2 to Cd1. The origin is at the center of mass of the seven atoms of the phenol group. Transition energies and intensities based upon parameters used by Chen and Woody (J. Am. Chem. Soc. 93, 29-37 (1971)).