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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Rotational Spectrum of the Dimethyl Ether-Acetylene Complex:Evidence for an Effective C_(2nu)Geometry
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Rotational Spectrum of the Dimethyl Ether-Acetylene Complex:Evidence for an Effective C_(2nu)Geometry

机译：二甲基醚-乙炔配合物的旋转光谱：有效C_（2nu）几何的证据

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The rotational spectra for five isotopomers of the 1:1 weakly bound complex formed between dimethyl ether(DME)and acetylene(HCCH)have been measured by Fourier transform microwave spectroscopy.The experimental rotational constants,planar moments,and dipole moment components are consistent with a floppy complex possessing an effective C_(2nu)structure in which the hydrogen atom of acetylene is hydrogen bonded to the oxygen atom of dimethyl ether with an intermolecular H...O separation of 2.08(3)A.Experimental rotational constants for the normal isotopic species are A = 10382.5(17)MHz,B = 1535.7187-(18)MHz,and C = 1328.3990(17)MHz and the dipole moment components are mu_a = mu_(total)= 1.91(10)D.Ab initio calculations at the MP2/6-31 l++G(2d,2p)level indicate that the energy barrier for motion of the HCCH subunit between the lone pairs of the DME,via a C_(2nu)intermediate structure,is very low(~0.29 kJ mol~(-1))-Inclusion of basis set superposition error and zero point energy corrections to the energies of four stationary points located on the potential energy surface shows that the relative stabilities are particularly sensitive to these corrections.The ab initio optimizations give rotational constants for the C_(2nu)structure of A = 10066 MHz,B = 1496 MHz,and C = 1324 MHz,and a dipole moment of mu_a = mu_(total)= 2.12 D,in reasonable agreement with the experimentally determined values.The structural parameters and energetics of the DME-HCCH complex will be discussed and compared to similar complexes such as H_2O-HCCH.
机译：用傅立叶变换微波光谱法测量了二甲醚（DME）与乙炔（HCCH）之间形成的1：1弱键合配合物的五个同位素异构体的旋转光谱。实验旋转常数，平面矩和偶极矩成分与具有有效C_（2nu）结构的松散配合物，其中乙炔的氢原子氢键合到二甲醚的氧原子上，分子间的H ... O分离度为2.08（3）A。同位素种类为A = 10382.5（17）MHz，B = 1535.7187-（18）MHz，C = 1328.3990（17）MHz，偶极矩分量为mu_a = mu_（total）= 1.91（10）D.Ab从头算在MP2 / 6-31 l ++ G（2d，2p）水平上，表明通过C_（2nu）中间结构，DME孤对之间HCCH亚基运动的能垒非常低（〜 0.29 kJ mol〜（-1））-包括基组叠加误差和零点能量校正对势能表面上四个固定点的能量进行的分析表明，相对稳定性对这些校正特别敏感。从头算优化得出C_（2nu）结构的旋转常数为A = 10066 MHz，B = 1496 MHz， C = 1324 MHz，偶极矩mu_a = mu_（total）= 2.12 D，与实验确定的值合理吻合。将讨论DME-HCCH配合物的结构参数和能量，并将其与类似配合物进行比较作为H_2O-HCCH。

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