Czarnik-Matusewicz B, Chandra AK, Zeegers-Huyskens T
Faculty of Chemistry, University of Wroclaw, 14 Joliot-Curie Street, Wroclaw, 50 383, Poland
J Mol Spectrosc. 1999 Jun;195(2):308-316. doi: 10.1006/jmsp.1999.7818.
Geometric and vibrational spectroscopic data (bond distances and angles, vibrational frequencies, infrared intensities) of pentachlorophenol-OH (PCP-OH) and pentachlorophenol-OD (PCP-OD) are calculated by density functional theory (B3LYP) using the 6-311G(d, p) basis set. Except for the vibrations involving the OH bond, the agreement between the experimental and calculated fundamental frequencies between 3600 and 400 cm-1 is very good. The theoretical method failed, however, to reproduce quantitatively the experimental intensities. The infrared spectra between 3600 and 10 000 cm-1 are studied, and the overtones or combination bands are assigned by comparing the spectra of PCP-OH and PCP-OD. The difference between the experimental and theoretical frequencies of the nu(OH) and nu(OD) frequencies can be mainly accounted for by the neglect of the anharmonicities of these vibrations in calculations. The binary or ternary combinations characterized by the highest coupling constants and the highest intensities are those involving the nu(OH), delta(OH), gamma(OH), and nu(C-O) vibrations. Copyright 1999 Academic Press.
采用密度泛函理论（B3LYP）并使用6 - 311G(d, p)基组计算了五氯苯酚 - OH（PCP - OH）和五氯苯酚 - OD（PCP - OD）的几何和振动光谱数据（键长和键角、振动频率、红外强度）。除了涉及OH键的振动外，实验值与计算得到的3600至400 cm⁻¹之间的基频吻合得非常好。然而，该理论方法未能定量重现实验强度。研究了3600至10000 cm⁻¹之间的红外光谱，并通过比较PCP - OH和PCP - OD的光谱来归属泛音或组合带。计算中忽略了这些振动的非谐性，这主要导致了ν(OH)和ν(OD)频率的实验值与理论值之间的差异。具有最高耦合常数和最高强度的二元或三元组合是那些涉及ν(OH)、δ(OH)、γ(OH)和ν(C - O)振动的组合。版权所有1999年学术出版社。
