A monomeric complex of ammonia and cuprous chloride: H3N••CuCl isolated and characterised by rotational spectroscopy and ab initio calculations
A monomeric complex of ammonia and cuprous chloride: H3N••CuCl isolated and characterised by rotational spectroscopy and ab initio calculations
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DOI：
10.1063/1.4916391
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发表时间：
2015-04-14
影响因子：
4.4
通讯作者：
Legon, Anthony C.
中科院分区：
文献类型：
--
作者：
Bittner, Dror M.;Zaleski, Daniel P.;Legon, Anthony C.
在低浓度的NH3和CCl 4存在下，通过激光蒸发铜样品在气相中产生并分离H3 N中心点中心点CuCl单体。由此产生的复合物冷却到接近2 K的气体样品的超音速膨胀过程中的旋转温度，其特征在于7和18.5 GHz之间的宽带旋转光谱。测量和分析了六种同位素的光谱，以确定转动，B-0;离心畸变，D-J，D-JK;以及Cu，Cl和N-14核的核四极耦合常数，chi（aa）（X）。配合物的几何构型为C-3v，N、Cu和Cl原子位于a惯性轴上。通过几何参数与实验测定的转动惯量的拟合和CCSD（T）（F12*）/AVQZ水平上的从头计算，精确地计算了配合物中的键距和键角（H-N中心点Cu）。在r（0）几何中，r（Cu-Cl）、r（Cu-N）和角度（H-N中心点Cu）参数分别被评估为2.0614（7）埃、1.9182（13）埃和111.40（6）度，与从头计算良好一致。的几何参数评估孤立的复杂的比较与晶体学建立的固态样品[Cu（NH 3）Cl]。(C)2015 AIP Publishing LLC.
The H3N center dot center dot center dot CuCl monomer has been generated and isolated in the gas phase through laser vaporisation of a copper sample in the presence of low concentrations of NH3 and CCl4 in argon. The resulting complex cools to a rotational temperature approaching 2 K during supersonic expansion of the gas sample and is characterised by broadband rotational spectroscopy between 7 and 18.5 GHz. The spectra of six isotopologues are measured and analysed to determine rotational, B-0; centrifugal distortion, D-J, D-JK; and nuclear quadrupole coupling constants of Cu, Cl, and N-14 nuclei, chi(aa)(X). The geometry of the complex is C-3v with the N, Cu, and Cl atoms located on the a inertial axis. Bond distances and the angle(H-N center dot center dot center dot Cu) bond angle within the complex are precisely evaluated through fitting of geometrical parameters to the experimentally determined moments of inertia and through ab initio calculations at the CCSD(T)(F12*)/AVQZ level. The r(Cu-Cl), r(Cu-N), and angle(H-N center dot center dot center dot Cu) parameters are, respectively, evaluated to be 2.0614(7) angstrom, 1.9182(13) angstrom, and 111.40(6)degrees in the r(0) geometry, in good agreement with the ab initio calculations. Geometrical parameters evaluated for the isolated complex are compared with those established crystallographically for a solid-state sample of [Cu(NH3)Cl]. (C) 2015 AIP Publishing LLC.