Schmitt Michael, Böhm Marcel, Ratzer Christian, Krügler Daniel, Kleinermanns Karl, Kalkman Ivo, Berden Giel, Meerts W Leo
Institut für Physikalische Chemie, Universitätsstrasse 26.43.02, 40225 Düsseldorf, Germany.
Chemphyschem. 2006 Jun 12;7(6):1241-9. doi: 10.1002/cphc.200500670.
The rotationally resolved UV spectra of the electronic origins of five isotopomers of the phenol dimer have been measured. The complex spectra are analyzed using a fitting strategy based on a genetic algorithm. The intermolecular geometry parameters have been determined from the inertial parameters for both electronic states and compared to the results of ab initio calculations. In the electronic ground state, a larger hydrogen-bond length than in the ab initio calculations is found together with a smaller tilt angle of the aromatic rings, which shows a more pronounced dispersion interaction. In the electronically excited state, the hydrogen-bond length decreases, as has been found for other hydrogen-bonded clusters of phenol, and the two aromatic rings are tilted less toward each other.
已测量了苯酚二聚体五种同位素异构体电子基态的转动分辨紫外光谱。使用基于遗传算法的拟合策略对复杂光谱进行了分析。根据两个电子态的惯性参数确定了分子间几何参数，并与从头算结果进行了比较。在电子基态中，发现氢键长度比从头算计算结果更大，同时芳香环的倾斜角更小，这表明存在更显著的色散相互作用。在电子激发态中，氢键长度减小，这与其他苯酚氢键簇的情况相同，并且两个芳香环彼此间的倾斜度也减小。
