{"title":"十个新氟乙烯/CO2 簇 (C2H3F)x(CO2)y 的旋转光谱:以数据为中心的方法在复杂混合物光谱赋值中的应用","authors":"","doi":"10.1016/j.jms.2024.111938","DOIUrl":null,"url":null,"abstract":"<div><p>Chirped-pulse Fourier-transform microwave (CP-FTMW) spectroscopy has been used to measure the spectra of ten previously unobserved fluoroethylene (FE)/CO<sub>2</sub> clusters, (FE)<sub>x</sub>(CO<sub>2</sub>)<sub>y</sub>, with x from 1 to 4 and y from 0 to 4. Multiple spectra were recorded with varying concentrations of CO<sub>2</sub> in the sample, and at least 400,000 free induction decays averaged per data set. This allowed implementation of data-centered approaches, using intensity variation, to identify subsets of transitions belonging to the same cluster species or those of similar composition, simplifying the assignment process for the complex mixture of clusters present. All spectra were fitted to Watson <em>A</em>-reduction Hamiltonians, including quartic distortion constants, with very few species requiring higher order distortion constants for satisfactory fits to be obtained. Computational data at MP2/6-311++G(2d,2p) and <em>ω</em>B97X-D/6-31+G(d,p) levels suggested FE:CO<sub>2</sub> ratios and likely structural arrangements of each cluster based on comparisons with experimental rotational constants.</p></div>","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":1.4000,"publicationDate":"2024-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0022285224000651/pdfft?md5=2176ca31fb02fa6cd55c89dd81def90e&pid=1-s2.0-S0022285224000651-main.pdf","citationCount":"0","resultStr":"{\"title\":\"Rotational spectra of ten new fluoroethylene/CO2 clusters, (C2H3F)x(CO2)y: Application of data-centered methods to the assignment of spectra in complex mixtures\",\"authors\":\"\",\"doi\":\"10.1016/j.jms.2024.111938\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Chirped-pulse Fourier-transform microwave (CP-FTMW) spectroscopy has been used to measure the spectra of ten previously unobserved fluoroethylene (FE)/CO<sub>2</sub> clusters, (FE)<sub>x</sub>(CO<sub>2</sub>)<sub>y</sub>, with x from 1 to 4 and y from 0 to 4. Multiple spectra were recorded with varying concentrations of CO<sub>2</sub> in the sample, and at least 400,000 free induction decays averaged per data set. This allowed implementation of data-centered approaches, using intensity variation, to identify subsets of transitions belonging to the same cluster species or those of similar composition, simplifying the assignment process for the complex mixture of clusters present. All spectra were fitted to Watson <em>A</em>-reduction Hamiltonians, including quartic distortion constants, with very few species requiring higher order distortion constants for satisfactory fits to be obtained. Computational data at MP2/6-311++G(2d,2p) and <em>ω</em>B97X-D/6-31+G(d,p) levels suggested FE:CO<sub>2</sub> ratios and likely structural arrangements of each cluster based on comparisons with experimental rotational constants.</p></div>\",\"PeriodicalId\":16367,\"journal\":{\"name\":\"Journal of Molecular Spectroscopy\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.4000,\"publicationDate\":\"2024-09-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.sciencedirect.com/science/article/pii/S0022285224000651/pdfft?md5=2176ca31fb02fa6cd55c89dd81def90e&pid=1-s2.0-S0022285224000651-main.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Molecular Spectroscopy\",\"FirstCategoryId\":\"101\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0022285224000651\",\"RegionNum\":4,\"RegionCategory\":\"物理与天体物理\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"PHYSICS, ATOMIC, MOLECULAR & CHEMICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Molecular Spectroscopy","FirstCategoryId":"101","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022285224000651","RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"PHYSICS, ATOMIC, MOLECULAR & CHEMICAL","Score":null,"Total":0}
Rotational spectra of ten new fluoroethylene/CO2 clusters, (C2H3F)x(CO2)y: Application of data-centered methods to the assignment of spectra in complex mixtures
Chirped-pulse Fourier-transform microwave (CP-FTMW) spectroscopy has been used to measure the spectra of ten previously unobserved fluoroethylene (FE)/CO2 clusters, (FE)x(CO2)y, with x from 1 to 4 and y from 0 to 4. Multiple spectra were recorded with varying concentrations of CO2 in the sample, and at least 400,000 free induction decays averaged per data set. This allowed implementation of data-centered approaches, using intensity variation, to identify subsets of transitions belonging to the same cluster species or those of similar composition, simplifying the assignment process for the complex mixture of clusters present. All spectra were fitted to Watson A-reduction Hamiltonians, including quartic distortion constants, with very few species requiring higher order distortion constants for satisfactory fits to be obtained. Computational data at MP2/6-311++G(2d,2p) and ωB97X-D/6-31+G(d,p) levels suggested FE:CO2 ratios and likely structural arrangements of each cluster based on comparisons with experimental rotational constants.
期刊介绍:
The Journal of Molecular Spectroscopy presents experimental and theoretical articles on all subjects relevant to molecular spectroscopy and its modern applications. An international medium for the publication of some of the most significant research in the field, the Journal of Molecular Spectroscopy is an invaluable resource for astrophysicists, chemists, physicists, engineers, and others involved in molecular spectroscopy research and practice.