Сибирский федеральный университет

Тип публикации: статья из журнала

Год издания: 2019

Идентификатор DOI: 10.1021/acs.jpclett.9b02815

Аннотация: Cyclo[18]carbon (C-18) is studied computationally at the density functional theory (DFT) and ab initio levels to obtain insight into its electronic structure, aromaticity, and adsorption properties on a NaCl surface. DFT functionals with a small amount of Hartree-Fock exchange fail to determine the experimentally observed polyyne molecular structure, revealing a cumulene-type geometry. Exchange-correlation functionals with a large amount of Hartree-Fock exchange as well as ab initio CASSCF calculations yield the polyyne structure as the ground state and the cumulene structure as a transition state between the two inverted polyyne structures through a Kekule distortion. The polyyne and the cumulene structures are found to be doubly Huckel aromatic. The calculated adsorption energy of cyclo[18]carbon on the NaCl surface is small (37 meV/C) and almost the same for both structures, implying that the surface does not stabilize a particular geometry.

Журнал: JOURNAL OF PHYSICAL CHEMISTRY LETTERS

Выпуск журнала: Vol. 10, Is. 21

Номера страниц: 6701-6705

ISSN журнала: 19487185

Место издания: WASHINGTON

Издатель: AMER CHEMICAL SOC

• Baryshnikov Glib V. (KTH Royal Inst Technol, Sch Engn Sci Chem Biotechnol & Hlth, Div Theoret Chem & Biol, S-10691 Stockholm, Sweden; Bohdan Khmelnytsky Natl Univ, Dept Chem & Nanomat Sci, UA-18031 Cherkassy, Ukraine)
• Valiev Rashid R. (Natl Res Tomsk Polytech Univ, Res Sch Chem & Appl Biomed Sci, Lenin Ave 30, Tomsk 634050, Russia; Univ Helsinki, Fac Sci, Dept Chem, FIN-00014 Helsinki, Finland)
• Kuklin Artem V. (KTH Royal Inst Technol, Sch Engn Sci Chem Biotechnol & Hlth, Div Theoret Chem & Biol, S-10691 Stockholm, Sweden; Siberian Fed Univ, Div Theoret Phys & Wave Phenomena, 79 Svobodniy Av, Krasnoyarsk 660041, Russia)
• Sundholm Dage (Univ Helsinki, Fac Sci, Dept Chem, FIN-00014 Helsinki, Finland)
• Agren Hans (KTH Royal Inst Technol, Sch Engn Sci Chem Biotechnol & Hlth, Div Theoret Chem & Biol, S-10691 Stockholm, Sweden; Henan Univ, Coll Chem & Chem Engn, Kaifeng 475004, Henan, Peoples R ChinaArticle)

• Web of Science Core Collection