Competition between Hückel’s Rule and Jahn–Teller Distortion in Small Carbon Rings: A Quantum Monte Carlo Study

Hong, Iuegyun; Ahn, Jeonghwan; Shin, Hyeondeok; Bae, Hyeonhu; Lee, Hoonkyung; Benali, Anouar; Kwon, Yongkyung

doi:10.1021/acs.jpca.0c02577

Competition between Hückel’s Rule and Jahn–Teller Distortion in Small Carbon Rings: A Quantum Monte Carlo Study

Journal Article · Thu Apr 16 00:00:00 EDT 2020 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.0c02577· OSTI ID:1696911

^[1]; ^[1]; Shin, Hyeondeok ^[2]; ^[1]; ^[1]; ^[2]; ^[1]

Konkuk Univ., Seoul (South Korea)
Argonne National Lab. (ANL), Argonne, IL (United States)

Structural properties and energetics of carbon rings are studied with the diffusion Monte Carlo (DMC) method. Our DMC-based geometry optimization reveals that both polyynic C_4n and cumulenic C_4n+2 rings exhibit bond length alternations for n >= 3, which is understood to be due to Jahn-Teller distortions. The bond length alternation even in a cumulenic (4n + 2) carbon ring was experimentally observed in a recently synthesized C₁₈ molecule. From a comparison of the DMC cohesive energies of C_4n with those of C_{4n + 2}, we present a comprehensive picture of the competition between Huckel's rule and Jahn-Teller distortion in small carbon rings; the former is more dominant than the latter for n < 5 where C_{4n + 2} rings are more stable than C_4n, while C_4n rings are as stable as C_{4n + 2} for n < 5 where dimerization effects due to Jahn-Teller distortion are more important.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; AC05-00OR22725

OSTI ID:: 1696911

Alternate ID(s):: OSTI ID: 1720232

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 18 Vol. 124; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Competition between Hückel’s Rule and Jahn–Teller Distortion in Small Carbon Rings: A Quantum Monte Carlo Study

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