接枝到钙表面的分子结合能:周期性DFT研究

IF 3.2 3区 化学 Q2 CHEMISTRY, PHYSICAL
Pierre Beaujean, Benoît Champagne
{"title":"接枝到钙表面的分子结合能:周期性DFT研究","authors":"Pierre Beaujean, Benoît Champagne","doi":"10.1021/acs.jpcc.5c01160","DOIUrl":null,"url":null,"abstract":"Understanding the spectroscopic signatures of solid-electrolyte interphase (SEI) components is crucial for advancing calcium-based batteries, as the SEI composition directly impacts the performance. X-ray photoelectron spectroscopy (XPS) is a key technique for probing surface chemistry, yet fundamental studies on binding energies of SEI-grafted molecules remain limited. Additionally, accurately computing XPS chemical shifts for surfaces and adsorbates while balancing precision and cost is a challenge. This work employs density functional theory (DFT) with periodic boundary conditions to investigate the adsorption of tetrahydrofuran (THF) and its degradation products on calcium surfaces, including metallic Ca, CaO, and CaH<sub>2</sub>. A fully hydroxylated CaO surface is also considered. Two primary interaction mechanisms are identified: (i) adsorption via unsaturated carbon atoms and (ii) proton transfer from alcohol groups to CaO. After evaluating various computational approaches, the Slater–Janak scheme is adopted to compute the XPS spectra for O 1s, C 1s, and Ca 2s. Significant shifts in oxygen and carbon binding energies are observed, while these of calcium remain largely unchanged. These findings provide valuable insights into SEI formation and offer useful trends for interpreting XPS spectra, with good agreement observed between simulations and available experimental data.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"16 1","pages":""},"PeriodicalIF":3.2000,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Binding Energies of Molecules Grafted onto Calcium Surfaces: A Periodic DFT Investigation\",\"authors\":\"Pierre Beaujean, Benoît Champagne\",\"doi\":\"10.1021/acs.jpcc.5c01160\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Understanding the spectroscopic signatures of solid-electrolyte interphase (SEI) components is crucial for advancing calcium-based batteries, as the SEI composition directly impacts the performance. X-ray photoelectron spectroscopy (XPS) is a key technique for probing surface chemistry, yet fundamental studies on binding energies of SEI-grafted molecules remain limited. Additionally, accurately computing XPS chemical shifts for surfaces and adsorbates while balancing precision and cost is a challenge. This work employs density functional theory (DFT) with periodic boundary conditions to investigate the adsorption of tetrahydrofuran (THF) and its degradation products on calcium surfaces, including metallic Ca, CaO, and CaH<sub>2</sub>. A fully hydroxylated CaO surface is also considered. Two primary interaction mechanisms are identified: (i) adsorption via unsaturated carbon atoms and (ii) proton transfer from alcohol groups to CaO. After evaluating various computational approaches, the Slater–Janak scheme is adopted to compute the XPS spectra for O 1s, C 1s, and Ca 2s. Significant shifts in oxygen and carbon binding energies are observed, while these of calcium remain largely unchanged. These findings provide valuable insights into SEI formation and offer useful trends for interpreting XPS spectra, with good agreement observed between simulations and available experimental data.\",\"PeriodicalId\":61,\"journal\":{\"name\":\"The Journal of Physical Chemistry C\",\"volume\":\"16 1\",\"pages\":\"\"},\"PeriodicalIF\":3.2000,\"publicationDate\":\"2025-05-05\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry C\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.jpcc.5c01160\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry C","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.jpcc.5c01160","RegionNum":3,"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

摘要

了解固体电解质间相(SEI)成分的光谱特征对于推进钙基电池的发展至关重要,因为SEI成分直接影响电池的性能。x射线光电子能谱(XPS)是探测表面化学的关键技术,但对sei接枝分子结合能的基础研究仍然有限。此外,在平衡精度和成本的同时,准确计算表面和吸附物的XPS化学位移也是一项挑战。本研究采用具有周期性边界条件的密度泛函理论(DFT)研究了四氢呋喃(THF)及其降解产物在钙表面的吸附,包括金属Ca、CaO和CaH2。也考虑了完全羟基化的CaO表面。确定了两种主要的相互作用机制:(i)通过不饱和碳原子吸附和(ii)质子从醇基团转移到CaO。在评估了各种计算方法后,采用Slater-Janak格式计算了O - 1s、C - 1s和Ca - 2s的XPS光谱。氧和碳的结合能发生了显著的变化,而钙的结合能基本保持不变。这些发现为SEI的形成提供了有价值的见解,并为解释XPS光谱提供了有用的趋势,在模拟和现有实验数据之间观察到很好的一致性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Binding Energies of Molecules Grafted onto Calcium Surfaces: A Periodic DFT Investigation

Binding Energies of Molecules Grafted onto Calcium Surfaces: A Periodic DFT Investigation
Understanding the spectroscopic signatures of solid-electrolyte interphase (SEI) components is crucial for advancing calcium-based batteries, as the SEI composition directly impacts the performance. X-ray photoelectron spectroscopy (XPS) is a key technique for probing surface chemistry, yet fundamental studies on binding energies of SEI-grafted molecules remain limited. Additionally, accurately computing XPS chemical shifts for surfaces and adsorbates while balancing precision and cost is a challenge. This work employs density functional theory (DFT) with periodic boundary conditions to investigate the adsorption of tetrahydrofuran (THF) and its degradation products on calcium surfaces, including metallic Ca, CaO, and CaH2. A fully hydroxylated CaO surface is also considered. Two primary interaction mechanisms are identified: (i) adsorption via unsaturated carbon atoms and (ii) proton transfer from alcohol groups to CaO. After evaluating various computational approaches, the Slater–Janak scheme is adopted to compute the XPS spectra for O 1s, C 1s, and Ca 2s. Significant shifts in oxygen and carbon binding energies are observed, while these of calcium remain largely unchanged. These findings provide valuable insights into SEI formation and offer useful trends for interpreting XPS spectra, with good agreement observed between simulations and available experimental data.
求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
The Journal of Physical Chemistry C
The Journal of Physical Chemistry C 化学-材料科学:综合
CiteScore
6.50
自引率
8.10%
发文量
2047
审稿时长
1.8 months
期刊介绍: The Journal of Physical Chemistry A/B/C is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信