Instituto de Química, Universidade Estadual de Campinas, Campinas, SP, Brazil.
Spectrochim Acta A Mol Biomol Spectrosc. 2010 Jan;75(1):461-5. doi: 10.1016/j.saa.2009.11.010. Epub 2009 Nov 13.
An extensive HF, MP2, B3LYP and CCSD study of the molecular structure, force field and normal vibrations has been carried out for the hydrogen cyanide compound with boron tribromide. Most of the calculations agree that the HCN-BBr(3) molecule belongs to C(3v) point group and has a N-B length of 1.55-1.70 A and a N-B-Br angle of 103-105 degrees. These calculations also have estimated the missing low-wavenumber fundamentals in the 190 (nu(5)), 150 (nu(9)) and 105 cm(-1) (nu(10)) regions, instead of the supposed fundamentals at 207, 188 and 150 cm(-1), respectively, based on the combination bands. The quantum chemical force constants, by the B3LYP/6-31G and CCSD/3-21G calculations, have been adjusted by the scaling factors to reproduce the fundamentals in the literature [3] to include the bands below 200 cm(-1) proposed in this study. Normal coordinate analysis using the scaled force constants has been performed to interpret the molecular vibrations of four isotopic molecules, HCN-(10)BBr(3), HCN-(11)BBr(3), DCN-(10)BBr(3) and DCN-(11)BBr(3).
已经对氢氰酸与三溴化硼化合物进行了广泛的 HF、MP2、B3LYP 和 CCSD 研究,以确定其分子结构、力场和正则振动。大多数计算都认为 HCN-BBr(3)分子属于 C(3v)点群,具有 1.55-1.70 A 的 N-B 长度和 103-105 度的 N-B-Br 角度。这些计算还估计了在 190(ν(5))、150(ν(9))和 105 cm(-1)(ν(10))区域缺失的低波数基本频率,而不是基于组合带的假定基本频率,分别为 207、188 和 150 cm(-1)。通过 B3LYP/6-31G 和 CCSD/3-21G 计算的量子化学力常数,通过调整比例因子以再现文献[3]中的基本频率来进行调整,以包括本研究中提出的低于 200 cm(-1)的带。使用比例力常数进行正则坐标分析,以解释四个同位素分子(HCN-(10)BBr(3)、HCN-(11)BBr(3)、DCN-(10)BBr(3)和 DCN-(11)BBr(3))的分子振动。