EXCITED-STATE POLARIZABILITIES AND DIPOLE-MOMENTS OF DIPHENYLPOLYENES AND RETINAL
EXCITED-STATE POLARIZABILITIES AND DIPOLE-MOMENTS OF DIPHENYLPOLYENES AND RETINAL
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DOI：
10.1021/j150643a010
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发表时间：
1983-01-01
影响因子：
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通讯作者：
MATHIES, R
中科院分区：
文献类型：
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作者：
PONDER, M;MATHIES, R
在聚甲基丙烯酸甲酯（PMM）薄膜中测量了全反式视网膜（ATR）的1BU激发态。长轴极化率提高了600±100Á3，偶极矩提高了13.2±0.6 d，利用椭球腔反应场模型将溶液极化率和偶极矩转换为气相值。在气相电子激发下，长轴极化率的增加为DPB 80±10 A3， DPH 127 db 6 A3, DPO 170±4 A3, DPD 210±20 A3, ATR 200±20 A3。由于视网膜的激发态极化率是如此之大，它的溶液，激发态偶极矩（19.8±0.7 D）到气相值（7±1 D）的转换涉及一个异常大的反应场因子。这些结果与提出的视觉色素和细菌视紫红质的最大吸收调节机制之间的关系
“1BU” excited state of all-trans-retinal (ATR) were measured inpoly (methyl methacrylate)(PMM) films. The long-axis polarizability increases by 600±100Á3 and the dipole moment increases by 13.2±0.6 D. These solution-phase polarizabilities and dipole moments were converted to gas-phase values by using an ellipsoidal cavity reaction field model. The increases in long-axis polarizability upon electronic excitation in the gas phase are 80±10 A3 for DPB, 127 db 6 A3 for DPH, 170±4 A3 for DPO, 210±20 A3 for DPD, and 200±20 A3 for ATR. Because theexcited-state polarizability of retinal is so large, the conversion of its solution-phase, excited-state dipole moment (19.8±0.7 D) to a gas-phase value (7±1 D) involves an unusually large reaction field factor. The relation of these results to proposed mechanisms for regulation of the absorption maximum in visual pigments and bacteriorhodopsin is