Probing the n ? p* carbonyl-carbonyl interactions in the formaldehyde-trifluoroacetone dimer by rotational spectroscopy

被引：4

作者：

Jin, Yan ^{[1
]}

Wang, Zhen ^{[1
]}

Li, Wenqin ^{[2
]}

Xu, Yugao ^{[1
]}

Feng, Gang ^{[1
]}

Lesarri, Alberto ^{[2
]}

Grabow, Jens-Uwe ^{[3
]}

机构：

[1] Chongqing Univ, Sch Chem & Chem Engn, Daxuecheng South Rd 55, Chongqing 401331, Peoples R China

[2] Univ Valladolid, Fac Ciencias IU, Dept Quim Fis & Quim Inorgan, CINQUIMA, Paseo Belen 7, Valladolid 47011, Spain

[3] Leibniz Univ Hannover, Inst Phys Chem & Elektrochem, Callinstr 3A, D-30167 Hannover, Germany

来源：

JOURNAL OF CHEMICAL PHYSICS | 2023年 / 158卷 / 12期

基金：

中国国家自然科学基金;

关键词：

MAIN-CHAIN ATOMS; MICROWAVE-SPECTRUM; GENERAL PROGRAM; REACTION PATHS; BASIS-SETS; HYDROGEN; FORCES; CONFORMATIONS; SPECTROMETER; SPLITTINGS;

D O I：

10.1063/5.0144298

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The non-covalent bonding features of carbonyl-carbonyl interactions have been investigated in the dimer of formaldehyde and trifluoroacetone using high resolution rotational spectroscopy combined with quantum chemical calculations. The observation of all possible isotopic substitutions for the heavy atoms in the complex enabled the determination of the accurate structure, characterized by the antiparallel arrangement of the two C=O bonds. The two moieties are connected through a dominant n ? p* interaction enhanced by one weak C-HMIDLINE HORIZONTAL ELLIPSISO hydrogen bond, as revealed by supporting natural bond orbital analysis and symmetry-adapted perturbation theory analysis. Further computational investigations on 17 related adducts stabilized by carbonyl-carbonyl n ? p* interactions show how the interaction strength is regulated by the incorporation of either electron-donating or withdrawing functional groups.

引用

页数：7

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