Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12, 11 158 Belgrade, Serbia.
J Phys Chem A. 2012 Jan 12;116(1):364-71. doi: 10.1021/jp209897y. Epub 2011 Dec 22.
Anharmonic force fields are a suitable means for identification of vibrational degrees of freedom responsible for the peculiar shape of molecular spectra and the existence of diverse relaxation pathways. In this contribution, we investigated interactions that govern the position of the O-H stretching band in phenol and its dimers with water and ammonia. Dominant couplings are identified, and the nature of relaxation channels is analyzed. The effect of hydrogen bonding on O-H stretching motion and vibrational energy redistribution time through intra- and intermolecular interactions is studied, and possible vibrational predissociation upon O-H stretch excitation is addressed. The results based on computed anharmonic force constants are in accord with the available experimental findings.
非谐力场是识别振动自由度的一种合适手段，这些振动自由度负责分子光谱的特殊形状和多种弛豫途径的存在。在本贡献中，我们研究了控制苯酚及其与水和氨形成的二聚体中 O-H 伸缩带位置的相互作用。确定了主要的耦合，并分析了弛豫通道的性质。研究了氢键对 O-H 伸缩运动的影响以及通过分子内和分子间相互作用进行振动能量再分配的时间，还讨论了 O-H 伸缩激发时可能发生的振动预解离。基于计算得到的非谐力常数的结果与现有的实验结果一致。
