Ziółkowski Marcin, Grabowski Sławomir J, Leszczynski Jerzy
Department of Quantum Chemistry, Institute of Chemistry, Nicolaus Copernicus University, 7, Gagarin St., 87-100 Toruń, Poland.
J Phys Chem A. 2006 May 25;110(20):6514-21. doi: 10.1021/jp060537k.
The H(2)CO...(HF)(n) (n = 1, ..., 9) complexes were investigated using the MP2 method and the following basis sets: 6-311++G(d,p), aug-cc-pVDZ and aug-cc-pVTZ. It was found that the cooperativity effect enhances significantly the F-H...O hydrogen bond; in some of cases one can detect the covalent nature of hydrogen bonding. To deepen the nature of the interactions investigated, the scheme of decomposition of the interaction energy was applied; for stronger H-bonds where the cooperativity is more important, the delocalization energy term increases. The ratio of delocalization energy to electrostatic energy increases for stronger hydrogen bonds where the proton...acceptor distance is shorter. The Bader theory was also applied, and it was found that for stronger H-bonds the electronic energy density at the proton...acceptor bond critical point is negative and may be attributed to the partly covalent interaction.
使用MP2方法和以下基组对H₂CO...(HF)ₙ（n = 1, ..., 9）配合物进行了研究：6-311++G(d,p)、aug-cc-pVDZ和aug-cc-pVTZ。结果发现，协同效应显著增强了F-H...O氢键；在某些情况下，可以检测到氢键的共价性质。为了深入研究相互作用的本质，应用了相互作用能分解方案；对于协同作用更重要的较强氢键，离域能项增加。对于质子...受体距离较短的较强氢键，离域能与静电能的比值增加。还应用了巴德理论，结果发现，对于较强氢键，质子...受体键临界点处的电子能量密度为负，这可能归因于部分共价相互作用。
