ELECTROOPTICAL ABSORPTION-MEASUREMENTS OF PHOTOTAUTOMERIZING SYSTEMS - S(0) AND S(1) STATIC POLARIZABILITIES OF BIPYRIDINEDIOLS

被引:105
作者
WORTMANN, R [1 ]
ELICH, K [1 ]
LEBUS, S [1 ]
LIPTAY, W [1 ]
BOROWICZ, P [1 ]
GRABOWSKA, A [1 ]
机构
[1] POLISH ACAD SCI,INST PHYS CHEM,PL-02124 WARSAW,POLAND
关键词
D O I
10.1021/j100203a029
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Ground- and excited-state polarizabilities of 2,2-bipyridine-3,3-diol (BP(OH)2), 5-methyl-2,2'-bipyridine-3,3'-diol (MeBP(OH)2), and 5,5'-dimethyl-2,2'-bipyridine-3,3'-diol (Me2BP(OH)2) were determined by means of dielectric, refractometric, and electrooptical absorption measurements. The ground-state polarizability tensor is anisotropic, the main component lying in the long molecular axis. Nuclear contributions to the static polarizability were found to be small (5-10%). The experimental ground-state polarizabilities are compared with results of semiempirical and ab initio quantum chemical calculations. Upon electronic excitation to the first excited singlet state, the polarizability increases by a factor of about 1.5, the change being exclusively parallel to the direction of the transition dipole (long axis). The Franck-Condon excited-state dipole moments of the centrosymmetrical compounds BP(OH)2 and Me2BP(OH)2 were confirmed to be zero within experimental error of 2 x 10(-30) cm (0.6 D). The experimental results support the notion of a symmetric double proton transfer taking place in the S1 state of bipyridinediols.
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页码:9724 / 9730
页数:7
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