摘要
A theoretical study on the blue-shifted H-bond N-H…O and red-shifted H-bond O-H…O in the complex HNO…H2O2 was conducted by employment of both standard and counterpoise-corrected methods to calculate the geometric structures and vibrational frequencies at the MP2/6-31G（d）, MP2/6-31 ＋ G（d,p）, MP2/6-311 ＋ ＋ G（d,p）, B3LYP/6-31G（d）, B3LYP/6-31 ＋G（d,p） and B3LYP/6-311 ＋ ＋G（d,p） levels. In the H-bond N-H…O, the calculated blue shift of N-H stretching frequency is in the vicinity of 120 cm^-1 and this is indeed the largest theoretical estimate of a blue shift in the X-H…Y H-bond ever reported in the literature. From the natural bond orbital analysis, the red-shifted H-bond O-H…O can be explained on the basis of the dominant role of the hyperconjugation. For the blue-shifted H-bond N-H…O, the hyperconjugation was inhibited due to the existence of significant electron density redistribution effect, and the large blue shift of the N-H stretching frequency was prominently due to the rehybridization of spn N-H hybrid orbital.
A theoretical study on the blue-shifted H-bond N-H…O and red-shifted H-bond O-H…O in the complex HNO…H2O2 was conducted by employment of both standard and counterpoise-corrected methods to calculate the geometric structures and vibrational frequencies at the MP2/6-31G（d）, MP2/6-31 ＋ G（d,p）, MP2/6-311 ＋ ＋ G（d,p）, B3LYP/6-31G（d）, B3LYP/6-31 ＋G（d,p） and B3LYP/6-311 ＋ ＋G（d,p） levels. In the H-bond N-H…O, the calculated blue shift of N-H stretching frequency is in the vicinity of 120 cm^-1 and this is indeed the largest theoretical estimate of a blue shift in the X-H…Y H-bond ever reported in the literature. From the natural bond orbital analysis, the red-shifted H-bond O-H…O can be explained on the basis of the dominant role of the hyperconjugation. For the blue-shifted H-bond N-H…O, the hyperconjugation was inhibited due to the existence of significant electron density redistribution effect, and the large blue shift of the N-H stretching frequency was prominently due to the rehybridization of spn N-H hybrid orbital.
基金
Project supported by the National Natural Science Foundation of China （No. G20477043） and Knowledge Creative Program of Chinese Academy of Sciences （No. KJCX2-SW-H08）.
