Energies of low-lying excited states of linear polyenes.
Energies of low-lying excited states of linear polyenes.
复制标题
线性多烯的低裂隙激发态的能量。
DOI：
10.1021/jp8060202
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发表时间：
2008-12-11
期刊：
影响因子：
--
通讯作者：
Frank HA
中科院分区：
文献类型：
--
作者：
Christensen RL;Galinato MG;Chu EF;Howard JN;Broene RD;Frank HA
在一系列非极性溶剂中获得了十碳四烯、十二五碳烯、十四碳六烯和十六碳七烯的全反式异构体的室温吸收和发射光谱。这些模型系统的光谱中解析的电子振动特征允许准确确定 S0 (11Ag-) → S2 (11Bu+) 和 S1 (21Ag–) → S0 (11Ag–) 电子起源作为溶剂极化率的函数。可以推断这些数据以预测在没有溶剂扰动的情况下的跃迁能量。末端甲基取代基对跃迁能的影响也可以估计。吸收和发射光谱中的 Franck-Condon 最大值用于估计 S0 (11Ag–) → S1 (21Ag–) 和 S0 (11Ag–) → S2 (11Bu+) 电子起源和“垂直”跃迁能量之间的差异。将真空中未取代的全反式多烯的垂直跃迁能量作为共轭长度的函数的实验估计与长期存在的多参考构型相互作用（MRCI）处理以及最近对 21Ag–（S2）和 11Bu+（S2）态能量的从头计算进行比较。
Room temperature absorption and emission spectra of the all-trans isomers of decatetraene, dodecapentaene, tetradecahexaene, and hexadecaheptaene have been obtained in a series of nonpolar solvents. The resolved vibronic features in the optical spectra of these model systems allow the accurate determination of S0 (11Ag-) → S2 (11Bu+) and S1 (21Ag–) → S0 (11Ag–) electronic origins as a function of solvent polarizability. These data can be extrapolated to predict the transition energies in the absence of solvent perturbations. The effects of the terminal methyl substituents on the transition energies also can be estimated. Franck–Condon maxima in the absorption and emission spectra were used to estimate differences between S0 (11Ag–) → S1 (21Ag–) and S0 (11Ag–) → S2 (11Bu+) electronic origins and “vertical” transition energies. Experimental estimates of the vertical transition energies of unsubstituted, all-trans polyenes in vacuum as a function of conjugation length are compared with long-standing multireference configuration interaction (MRCI) treatments and with more recent ab initio calculations of the energies of the 21Ag– (S2) and 11Bu+ (S2) states.
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影响因子：
4.4
作者：
ANDREWS, JR;HUDSON, BS
通讯作者：
HUDSON, BS
影响因子：
15
作者：
HUDSON, BS;RIDYARD, JNA;DIAMOND, J
通讯作者：
DIAMOND, J
影响因子：
4.4
作者：
KOHLER, BE
通讯作者：
KOHLER, BE
影响因子：
15
作者：
DAMICO, KL;MANOS, C;CHRISTENSEN, RL
通讯作者：
CHRISTENSEN, RL
影响因子：
1.8
作者：
Frank, HA;Chynwat, V;Bautista, J
通讯作者：
Bautista, J