The reaction coordinate of the S(1)-S(0) internal conversion of azulene has been analyzed using ab initio complete active space self-consistent field method. The stable geometry in S(0) (S(0) geometry) takes a bond-equalized structure where all the peripheral skeletal bond distances are similar to an aromatic CC bond distance. The transannular bond is similar to a normal C-C single bond. The first event upon electronic excitation into S(1) at S(0) geometry is characterized by the following two simultaneous changes in the skeletal bonds; the transannular bond in S(1) increases its double bond character and the aromaticity of the peripheral bonds disappears. In consequence, the most stable azulene in S(1) (S(1) geometry) has a biradical character. To reach the conical intersection between S(1) and S(0) (S(1)S(0)-CIX) where radiationless relaxation takes place, the seven-membered ring greatly deviates from a planar structure. After a transition into S(0) at S(1)S(0)-CIX, the bond-equalized structure is recovered immediately and then the nonplanarity decreases so that azulene again takes the stable planar S(0) geometry. In order to deepen the understanding of the S(1)-S(0) internal conversion, the dipole moments along the reaction coordinate have been analyzed.
Dermatological tests and examinations of the hand(s) were carried out in vibration-exposed and unexposed males. The subjects were 179 chain-saw workers in private forestry companies and 205 local inhabitants who had never used vibrating tools. The prevalences of Raynaud's phenomenon (RP), sclerodactylia, and edema of the hands were estimated in both groups, and associations between these cutaneous signs and vibration exposure were evaluated. The prevalences of RP and edema in the exposed group were 9.5% and 1.7%, respectively, and in the unexposed group, 2.9% and 1.5%, respectively. Sclerodactylia was seen in 31.8% of the chain-saw workers but in only 6.4% of the unexposed individuals. In statistical analyses based on unconditional logistic regression models with adjustment for age, RP was associated with long-term (> or = 20 years) vibration exposure [odds ratio (OR) = 7.06; 95% confidence interval (CI) = 2.51-19.87]. Sclerodactylia was associated with both short- and long-term vibration exposure (OR = 6.54, CI = 3.30-13.36; OR = 7.05; CI = 3.41-14.60, respectively). There were significant dose-response relationships between RP and duration of exposure and between sclerodactylia and duration of exposure. Results of function tests indicated a longer recovery time and a higher vibration threshold for the workers with RP. The presence of sclerodactylia, however, did not have any significant influence on function test results. It is possible to conclude that not only RP but also sclerodactylia could be induced by vibration exposure. However, most cases of sclerodactylia were not so serious as to involve disturbances of peripheral circulatory and nerve function.
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