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

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

doi:10.1021/acs.jpca.0c02577

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

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

Research output: Contribution to journal › Article › peer-review

15 Scopus citations

Abstract

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 Hückel'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.

Original language	English
Pages (from-to)	3636-3640
Number of pages	5
Journal	Journal of Physical Chemistry A
Volume	124
Issue number	18
DOIs	https://doi.org/10.1021/acs.jpca.0c02577
State	Published - May 7 2020
Externally published	Yes

Funding

We thank Dr. Shulenburger and Dr. Applencourt for very productive discussions. Y.K. was supported by the Basic Science Research Program (2018R1D1A1B07042443) through the National Research Foundation of Korea. A.B. and H.S. were supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division, as part of the Computational Materials Sciences Program and Center for Predictive Simulation of Functional Materials. We acknowledge the support from the Korea Institute of Science and Technology Information with supercomputing resources (KSC-2018-CHA-0053) that were used for DFT calculations. DMC calculations used an award of computer time provided by the Innovative and Novel Computational Impact on Theory and Experiment (INCITE) program using resources of the Argonne Leadership Computing Facility, which is a DOE Office of Science User Facility supported under contract DE-AC02-06CH11357.

Funders	Funder number
U.S. Department of Energy
Office of Science	DE-AC02-06CH11357
Basic Energy Sciences
Division of Materials Sciences and Engineering
Korea Institute of Science and Technology Information	KSC-2018-CHA-0053
National Research Foundation of Korea

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title = "Competition between H{\"u}ckel's Rule and Jahn-Teller Distortion in Small Carbon Rings: A Quantum Monte Carlo Study",

abstract = "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 C4n and cumulenic C4n + 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 C4n with those of C4n + 2, we present a comprehensive picture of the competition between H{\"u}ckel's rule and Jahn-Teller distortion in small carbon rings; the former is more dominant than the latter for n < 5 where C4n + 2 rings are more stable than C4n, while C4n rings are as stable as C4n + 2 for n < 5 where dimerization effects due to Jahn-Teller distortion are more important.",

author = "Iuegyun Hong and Jeonghwan Ahn and Hyeondeok Shin and Hyeonhu Bae and Hoonkyung Lee and Anouar Benali and Yongkyung Kwon",

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AU - Hong, Iuegyun

AU - Ahn, Jeonghwan

AU - Shin, Hyeondeok

AU - Bae, Hyeonhu

AU - Lee, Hoonkyung

AU - Benali, Anouar

AU - Kwon, Yongkyung

PY - 2020/5/7

Y1 - 2020/5/7

N2 - 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 C4n and cumulenic C4n + 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 C4n with those of C4n + 2, we present a comprehensive picture of the competition between Hückel's rule and Jahn-Teller distortion in small carbon rings; the former is more dominant than the latter for n < 5 where C4n + 2 rings are more stable than C4n, while C4n rings are as stable as C4n + 2 for n < 5 where dimerization effects due to Jahn-Teller distortion are more important.

AB - 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 C4n and cumulenic C4n + 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 C4n with those of C4n + 2, we present a comprehensive picture of the competition between Hückel's rule and Jahn-Teller distortion in small carbon rings; the former is more dominant than the latter for n < 5 where C4n + 2 rings are more stable than C4n, while C4n rings are as stable as C4n + 2 for n < 5 where dimerization effects due to Jahn-Teller distortion are more important.

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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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