Isomer-selected ion-molecule reactions of acetylene cations with propyne and allene

被引:15
作者
Schmid, P. C. [1 ,2 ,3 ]
Greenberg, J. [1 ,2 ]
Nguyen, T. L. [4 ,5 ]
Thorpe, J. H. [4 ,5 ]
Catani, K. J. [1 ,2 ]
Krohn, O. A. [1 ,2 ]
Miller, M., I [1 ,2 ]
Stanton, J. F. [4 ,5 ]
Lewandowski, H. J. [1 ,2 ]
机构
[1] Univ Colorado, JILA, Boulder, CO 80309 USA
[2] Univ Colorado, Dept Phys, Boulder, CO 80309 USA
[3] Univ Cologne, Phys Inst 1, Zulpicher Str 77, D-50937 Cologne, Germany
[4] Univ Florida, Dept Chem, Quantum Theory Project, Gainesville, FL 32611 USA
[5] Univ Florida, Dept Phys, Quantum Theory Project, Gainesville, FL 32611 USA
基金
美国国家科学基金会;
关键词
CHEMICAL-REACTIONS; COLD; IONIZATION; RESONANCE; CHEMISTRY; DYNAMICS; KINETICS;
D O I
10.1039/d0cp03953e
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
One of the fundamental goals of chemistry is to determine how molecular structure influences interactions and leads to different reaction products. Studies of isomer-selected and resolved chemical reactions can shed light directly on how form leads to function. In the following, we present the results of gas-phase reactions between acetylene cations (C2D2+) with two different isomers of C3H4: propyne (DC3D3) and allene (H2C3H2). Our highly controlled, trapped-ion environment allows for precise determination of reaction products and kinetics. From these results, we can infer details of the underlying reaction dynamics of C2H2++ C3H4. Through the synergy of experimental results and high-level quantum chemical potential energy surface calculations, we are able to identify distinct reaction mechanisms for the two isomers. We find long-range charge exchange with no complex formation is favored for allene, whereas charge exchange leads to an intermediate reaction complex for propyne and thus, different products. Therefore, this reaction displays a pronounced isomer-selective bi-molecular reactive process.
引用
收藏
页码:20303 / 20310
页数:8
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