Polyaromatic hydrocarbons with an imperfect aromatic system as catalysts of interstellar H2 formation

被引:3
作者
Jelenfi, David P. [1 ,2 ]
Schneiker, Anita [1 ,3 ]
Tajti, Attila [2 ]
Magyarfalvi, Gabor [3 ]
Tarczay, Gyorgy [3 ,4 ]
机构
[1] Eotvos Lorand Univ, Hevesy Gyorgy PhD Sch Chem, Budapest, Hungary
[2] Eotvos Lorand Univ, Inst Chem, Lab Theoret Chem, Budapest, Hungary
[3] Eotvos Lorand Univ, Inst Chem, Lab Mol Spect, POB 32, H-1518 Budapest, Hungary
[4] MTA ELTE Lendulet Lab Astrochem Res Grp, POB 32, H-1518 Budapest, Hungary
关键词
H atom tunnelling; instanton theory; astrochemistry; polyaromatic hydrocarbons; interstellar H-2 formation; MOLECULAR-HYDROGEN FORMATION; TRANSITION-STATE THEORY; PHASE; CHEMISORPTION; CONSTRAINTS; PHENALENE;
D O I
10.1080/00268976.2022.2142168
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
Although H-2 is the simplest and the most abundant molecule in the Universe, its formation in the interstellar medium, especially in the photodissociation regions is far from being fully understood. According to suggestions, the formation of H-2 is catalysed by polyaromatic hydrocarbons (PAHs) on the surface of interstellar grains. In the present study we have investigated the catalytic effect of small PAHs with an imperfect aromatic system. Quantum chemical computations were performed for the H-atom-abstraction and H-atom-addition reactions of benzene, cyclopentadiene, cycloheptatriene, indene, and 1H-phenalene. Heights of reaction barriers and tunnelling reaction rate constants were computed with density functional theory using the MPWB1K functional. For each molecule, the reaction path and the rate constants were determined at 50 K using ring-polymer instanton theory, and the temperature dependence of the rate constants was investigated for cyclopentadiene and cycloheptatriene. The computational results reveal that defects in the aromatic system compared to benzene can increase the rate of the catalytic H-2 formation at 50 K. [GRAPHICS] .
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页数:12
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