Anna H. James, Martina Kaledin* and Alexey L. Kaledin*,
{"title":"芳香族环b[10]碳中伪Jahn-Teller效应的第一性原理路径积分蒙特卡罗研究","authors":"Anna H. James, Martina Kaledin* and Alexey L. Kaledin*, ","doi":"10.1021/acs.jpca.4c0862010.1021/acs.jpca.4c08620","DOIUrl":null,"url":null,"abstract":"<p >There has been renewed interest in carbon nanoscale structures. Experimental measurements at 4.7 K and subsequent first-principles-based vibrational diffusion Monte Carlo simulations at 0 K recently showed that the aromatic cyclo[10]carbon prefers a <i>D</i><sub>5<i>h</i></sub> pentagon-like structure to a regular <i>D</i><sub>10<i>h</i></sub> decagon. This symmetry breaking is due to the second-order Jahn–Teller effect (JTE) and has been amply described in the literature for the cumulenic cyclo[4<i>m</i> + 2]carbon clusters. Yet temperature dependence of the JTE in cyclo[4<i>m</i> + 2]carbon clusters in general and the cyclo[10]carbon in particular has not been studied systematically. In this work, we employ path integral Monte Carlo simulations on a first-principles-derived permutationally invariant potential energy surface (PES) to examine the JTE in cyclo[10]carbon as a function of temperature. The PES was trained on a set of τHCTH/cc-pVQZ energies sampled up to ∼7.7 eV above the <i>D</i><sub>5<i>h</i></sub> global minimum and locally adjusted to a high-level benchmark (reported by others) of the 812 cm<sup>–1</sup> electronic energy difference between the <i>D</i><sub>5<i>h</i></sub> global minimum and the <i>D</i><sub>10<i>h</i></sub> transition state. The calculations show a strong JTE at lower temperatures with a dominant <i>D</i><sub>5<i>h</i></sub> composition at 100 K and a gradually diminishing JTE at higher temperatures with a washed-out pentagonal structure above 300 K.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 9","pages":"2238–2246 2238–2246"},"PeriodicalIF":2.8000,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpca.4c08620","citationCount":"0","resultStr":"{\"title\":\"First-Principles Path Integral Monte Carlo Studies of the Pseudo Jahn–Teller Effect in the Aromatic Cyclo[10]carbon\",\"authors\":\"Anna H. James, Martina Kaledin* and Alexey L. Kaledin*, \",\"doi\":\"10.1021/acs.jpca.4c0862010.1021/acs.jpca.4c08620\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >There has been renewed interest in carbon nanoscale structures. Experimental measurements at 4.7 K and subsequent first-principles-based vibrational diffusion Monte Carlo simulations at 0 K recently showed that the aromatic cyclo[10]carbon prefers a <i>D</i><sub>5<i>h</i></sub> pentagon-like structure to a regular <i>D</i><sub>10<i>h</i></sub> decagon. This symmetry breaking is due to the second-order Jahn–Teller effect (JTE) and has been amply described in the literature for the cumulenic cyclo[4<i>m</i> + 2]carbon clusters. Yet temperature dependence of the JTE in cyclo[4<i>m</i> + 2]carbon clusters in general and the cyclo[10]carbon in particular has not been studied systematically. In this work, we employ path integral Monte Carlo simulations on a first-principles-derived permutationally invariant potential energy surface (PES) to examine the JTE in cyclo[10]carbon as a function of temperature. The PES was trained on a set of τHCTH/cc-pVQZ energies sampled up to ∼7.7 eV above the <i>D</i><sub>5<i>h</i></sub> global minimum and locally adjusted to a high-level benchmark (reported by others) of the 812 cm<sup>–1</sup> electronic energy difference between the <i>D</i><sub>5<i>h</i></sub> global minimum and the <i>D</i><sub>10<i>h</i></sub> transition state. The calculations show a strong JTE at lower temperatures with a dominant <i>D</i><sub>5<i>h</i></sub> composition at 100 K and a gradually diminishing JTE at higher temperatures with a washed-out pentagonal structure above 300 K.</p>\",\"PeriodicalId\":59,\"journal\":{\"name\":\"The Journal of Physical Chemistry A\",\"volume\":\"129 9\",\"pages\":\"2238–2246 2238–2246\"},\"PeriodicalIF\":2.8000,\"publicationDate\":\"2025-02-24\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/acs.jpca.4c08620\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry A\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.jpca.4c08620\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry A","FirstCategoryId":"1","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jpca.4c08620","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
First-Principles Path Integral Monte Carlo Studies of the Pseudo Jahn–Teller Effect in the Aromatic Cyclo[10]carbon
There has been renewed interest in carbon nanoscale structures. Experimental measurements at 4.7 K and subsequent first-principles-based vibrational diffusion Monte Carlo simulations at 0 K recently showed that the aromatic cyclo[10]carbon prefers a D5h pentagon-like structure to a regular D10h decagon. This symmetry breaking is due to the second-order Jahn–Teller effect (JTE) and has been amply described in the literature for the cumulenic cyclo[4m + 2]carbon clusters. Yet temperature dependence of the JTE in cyclo[4m + 2]carbon clusters in general and the cyclo[10]carbon in particular has not been studied systematically. In this work, we employ path integral Monte Carlo simulations on a first-principles-derived permutationally invariant potential energy surface (PES) to examine the JTE in cyclo[10]carbon as a function of temperature. The PES was trained on a set of τHCTH/cc-pVQZ energies sampled up to ∼7.7 eV above the D5h global minimum and locally adjusted to a high-level benchmark (reported by others) of the 812 cm–1 electronic energy difference between the D5h global minimum and the D10h transition state. The calculations show a strong JTE at lower temperatures with a dominant D5h composition at 100 K and a gradually diminishing JTE at higher temperatures with a washed-out pentagonal structure above 300 K.
期刊介绍:
The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.