{"title":"Extracting Thermodynamic Properties of Carbyne from Tip-Enhanced Raman Scattering Images","authors":"Lun Yao, Hai-Zhen Yu, Zhen Xie* and Sai Duan*, ","doi":"10.1021/acs.jpclett.4c0227410.1021/acs.jpclett.4c02274","DOIUrl":null,"url":null,"abstract":"<p >The measurement of thermodynamic properties for nanosystems is essential to comprehend the inherent characteristics of nanomaterials. Traditional spectroscopy measurements, such as Raman or ultraviolet–visible spectroscopies, are limited to offering insights near the Γ point in the Brillouin zone and thus cannot precisely determine the system’s thermodynamic properties, for example, heat capacity. Utilizing the intrinsic broad momentum distribution in highly confined plasmonic fields, here we take <i>sp</i>-hybridized carbyne as a proof-of-the-principle example to show that ultrahigh-resolution tip-enhanced Raman scattering (TERS) images have the ability to access all <i>k</i>-points in the phonon Brillouin zone of one-dimensional nanosystems, allowing the comprehensive determination of vibrational features and heat capacity for finite carbon chains. Comparing phonon dispersion spectra and heat capacities under different boundary conditions, i.e., linear carbon chains and cyclic carbon molecules, we find that the heat capacities of linear structures converge more rapidly than the counterparts of cyclic structures to the benchmark of ideal carbyne. We also study the effects of different terminal groups in linear structures as well as the aromaticity in cyclic structures on heat capacity. This study provides a practical method for characterizing the thermodynamic properties of nanosystems, demonstrating the potential applications of TERS imaging in nanomaterial science.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":4.8000,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry Letters","FirstCategoryId":"1","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jpclett.4c02274","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
The measurement of thermodynamic properties for nanosystems is essential to comprehend the inherent characteristics of nanomaterials. Traditional spectroscopy measurements, such as Raman or ultraviolet–visible spectroscopies, are limited to offering insights near the Γ point in the Brillouin zone and thus cannot precisely determine the system’s thermodynamic properties, for example, heat capacity. Utilizing the intrinsic broad momentum distribution in highly confined plasmonic fields, here we take sp-hybridized carbyne as a proof-of-the-principle example to show that ultrahigh-resolution tip-enhanced Raman scattering (TERS) images have the ability to access all k-points in the phonon Brillouin zone of one-dimensional nanosystems, allowing the comprehensive determination of vibrational features and heat capacity for finite carbon chains. Comparing phonon dispersion spectra and heat capacities under different boundary conditions, i.e., linear carbon chains and cyclic carbon molecules, we find that the heat capacities of linear structures converge more rapidly than the counterparts of cyclic structures to the benchmark of ideal carbyne. We also study the effects of different terminal groups in linear structures as well as the aromaticity in cyclic structures on heat capacity. This study provides a practical method for characterizing the thermodynamic properties of nanosystems, demonstrating the potential applications of TERS imaging in nanomaterial science.
测量纳米系统的热力学性质对于了解纳米材料的固有特性至关重要。传统的光谱测量方法,如拉曼光谱或紫外-可见光谱,只能深入了解布里渊区Γ点附近的情况,因此无法精确测定系统的热力学性质,如热容量。利用高约束质子场中固有的宽动量分布,我们在此以sp-杂化氘代碳为例,证明超高分辨率的尖端增强拉曼散射(TERS)图像能够进入一维纳米系统声子布里渊区的所有k点,从而全面测定有限碳链的振动特征和热容量。通过比较不同边界条件(即线性碳链和环状碳分子)下的声子色散谱和热容量,我们发现线性结构的热容量比环状结构的热容量更快地趋近于理想碳链的基准。我们还研究了线性结构中不同末端基团以及环状结构中芳香性对热容量的影响。这项研究为表征纳米系统的热力学性质提供了一种实用方法,展示了 TERS 成像在纳米材料科学中的潜在应用。
期刊介绍:
The Journal of Physical Chemistry (JPC) Letters is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, chemical physicists, physicists, material scientists, and engineers. An important criterion for acceptance is that the paper reports a significant scientific advance and/or physical insight such that rapid publication is essential. Two issues of JPC Letters are published each month.