气相中HOCl和O_3分子间氯键和氢键的结构和性质(英文)

The structure and properties of the chlorine bond and hydrogen bond between HOCl and O_3 in gas phase

在DFT-B3LYP/6-311++G**水平上分别求得O3…ClOH氯键复合物和O3…HOCl氢键复合物势能面上的稳定构型.频率分析表明,与单体HOCl相比,分别在两种复合物中,Cl4-O5和H6-O5键伸缩振动频率发生红移,红移值分别为5.70和76.44 cm-1.经MP2/6-311++G**水平计算的含BSSE和零点振动能校正的气相中相互作用能分别为-2.102和-4.920 kJ.mol-1.NBO分析表明,在O3…ClOH氯键复合物中,引起Cl4-O5键变长的因素包括2种电荷转移:(1)LP(O1)1→σ*(Cl4-O5);(2)LP(O1)2→σ*(Cl4-O5),其中LP(O1)2→σ*(Cl4-O5)转移占主要作用,总的结果是使σ*(Cl10-O11)的自然布居数增加了14.44 me;在O3…HOCl氢键复合物中也存在类似的电荷转移,结果使σ*(H6-O5)的自然布居数增加了18.09 me.NRT理论进行键序分析表明,在氯键复合物和氢键复合物中,Cl4-O5和H6-O5键的键序都减小,与红外光谱频率计算分析和NBO分析的结论一致.AIM理论分析表明,分别在两种复合物中,O1…Cl4间和O1…H6间都存在键鞍点,而且O1…Cl4和O1…H6的ρ(r)都较小,分别为0.0111和0.0152 a.u.,说明复合物中的氯键和氢键相互作用较弱.另外,O1…Cl4氯键和O1…H6氢键的Lapla-cian量2ρ(r)分别为0.0479和0.0641 a.u.,都是较小的正值,说明这两种相互作用都以静电作用为主.

The optimized stable O3…ClOH chlorine bond complex and O3…HOCl hydrogen bond complex were found on the potential energy surface using density function theory （DFT） method at B3LYP/6-311＋＋G^＊＊ level. The red shifts of the O5-Cl4（Δυ=5.70cm^-1） and H6-O5 （Δυ=76.44 cm^-1） stretch vibration in halogen bond complex and hydrogen bond complex were obtained via frequency analysis, respectively. The chlorine bond and hydrogen bond interaction energies which were calculated with basis set superposition error（BSSE）and zero point vibrational energy （ZPE） correction were -2.102 and -4.920kJ·mol^-1 （MP2）. Nature bond orbit （NBO） analysis showed that two kinds of charge transfer exist in chlorine bond complex： （1） LP（O1）^1→σ^＊（Cl4-O5）; （2） LP（O1）^2→σ^＊（Cl4-O5）, and the nature population of the σ^＊（Cl4-O5） increased 14.44me. Analogous charge transfers exist in hydrogen bond complex, and the nature population of the σ^＊（H6-O5） increased 18.09me. Bond order analysis with nature resonance theory （NRT） showed that Cl4-O5 and H6-O5 bond order decreased in chlorine bond complex and hydrogen bond complex, respectively. This agrees with the charge transfer discussion and frequency analysis. The topological properties of the chlorine bond and hydrogen bond structures were also investigated by the atom-in-molecules （AIM） theory.