Dimitrova Yordanka, Slavova Iva
Institute of Organic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., 1113 Sofia, Bulgaria.
Spectrochim Acta A Mol Biomol Spectrosc. 2005 Jul;61(9):2095-102. doi: 10.1016/j.saa.2004.07.038.
The vibrational spectra of the binary complexes formed by HONO-trans and HONO-cis with dimethyl and diethyl ethers have been investigated using ab initio calculations at the SCF and MP2 levels with 6-311++G(d,p) basis set and B3LYP calculations with 6-31G(d,p) and 6-31+G(d,p) basis sets. Full geometry optimisation was made for the complexes studied. The accuracy of the ab initio calculations have been estimated by comparison between the predicted values of the vibrational characteristics (vibrational frequencies and infrared intensities) and the available experimental data. It was established, that the methods, used in this study are well adapted to the problem under examination. The predicted values with the B3LYP calculations are very near to the results, obtained with 6-311++G(d,p)/MP2. The ab initio and DFT calculations show that the changes in the vibrational characteristics (vibrational frequencies and infrared intensities) upon hydrogen bonding for the hydrogen-bonded complex (CH3)2O...HONO-trans are larger than for the complex (CH3)2O...HONO-cis.
利用在SCF和MP2水平下采用6-311++G(d,p)基组的从头算以及在6-31G(d,p)和6-31+G(d,p)基组下的B3LYP计算，研究了HONO-反式和顺式与二甲醚和二乙醚形成的二元配合物的振动光谱。对所研究的配合物进行了完全几何优化。通过比较振动特性（振动频率和红外强度）的预测值与现有实验数据，估计了从头算的准确性。结果表明，本研究中使用的方法非常适合所研究的问题。B3LYP计算的预测值与6-311++G(d,p)/MP2得到的结果非常接近。从头算和DFT计算表明，氢键配合物(CH3)2O...HONO-反式中氢键作用下振动特性（振动频率和红外强度）的变化大于配合物(CH3)2O...HONO-顺式。
