Loading…

Fermi Resonance Effects in the Vibrational Spectroscopy of Methyl and Methoxy Groups

A theoretical model Hamiltonian [J. Chem. Phys. 2013, 138, 064308] for describing vibrational spectra associated with the CH stretch of CH2 groups is extended to molecules containing methyl and methoxy groups. Results are compared to the infrared (IR) spectroscopy of four molecules studied under sup...

Full description

Saved in:
Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2014-11, Vol.118 (47), p.11272-11281
Main Authors: Sibert, Edwin L, Tabor, Daniel P, Kidwell, Nathanael M, Dean, Jacob C, Zwier, Timothy S
Format: Article
Language:English
Subjects:
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
cited_by cdi_FETCH-LOGICAL-a414t-ea32887c421f1bc262addf35834600d922e2f64b6e0201d6c198eac818b27c903
cites cdi_FETCH-LOGICAL-a414t-ea32887c421f1bc262addf35834600d922e2f64b6e0201d6c198eac818b27c903
container_end_page 11281
container_issue 47
container_start_page 11272
container_title The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory
container_volume 118
creator Sibert, Edwin L
Tabor, Daniel P
Kidwell, Nathanael M
Dean, Jacob C
Zwier, Timothy S
description A theoretical model Hamiltonian [J. Chem. Phys. 2013, 138, 064308] for describing vibrational spectra associated with the CH stretch of CH2 groups is extended to molecules containing methyl and methoxy groups. Results are compared to the infrared (IR) spectroscopy of four molecules studied under supersonic expansion cooling in gas phase conditions. The molecules include 1,1-diphenylethane (DPE), 1,1-diphenylpropane (DPP), 2-methoxyphenol (guaiacol), and 1,3-dimethoxy-2-hydroxybenzene (syringol). Transforming the bending normal mode vibrations of CH3 groups to local scissor vibrations leads to model Hamiltonians which share many features present in our model Hamiltonian for the stretching vibrations of CH2 Fermi coupled to scissor modes. The central difference arises from the greater scissor–scissor coupling present in the CH3 case. Comparing anharmonic couplings between these modes and the stretch–bend Fermi coupling for a variety of systems, it is observed that the anharmonic couplings are robust; their values are similar for the four molecules studied as well as for ethane and methanol. Similar results are obtained with both density functional theory and coupled-cluster calculations. This robustness suggests a new parametrization of the model Hamiltonian that reduces the number of fitting parameters. In contrast, the harmonic contributions to the Hamiltonian vary substantially between the molecules leading to important changes in the spectra. The resulting Hamiltonian predicts most of the major spectral features considered in this study and provides insights into mode mixing and the consequences of the mixing on dynamical processes that follow ultrafast CH stretch excitation.
doi_str_mv 10.1021/jp510142g
format article
fullrecord <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_1762062234</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>1628529156</sourcerecordid><originalsourceid>FETCH-LOGICAL-a414t-ea32887c421f1bc262addf35834600d922e2f64b6e0201d6c198eac818b27c903</originalsourceid><addsrcrecordid>eNqFkE1LxDAURYMoOo4u_AOSjaCL6nsvbdouZZhRQRH82pY0TbVD29SkBeffWx2dleDqXbiHC-8wdoRwjkB4sewiBAzpdYtNMCIIIsJoe8yQpEEkRbrH9r1fAgAKCnfZHkUiFgDphD0tjGsq_mC8bVWrDZ-XpdG951XL-zfDX6rcqb4ay5o_dmPjrNe2W3Fb8jvTv61qrtriO9qPFb9yduj8AdspVe3N4c-dsufF_Gl2HdzeX93MLm8DFWLYB0YJSpJYh4Ql5pokqaIoRZSIUAIUKZGhUoa5NECAhdSYJkbpBJOcYp2CmLLT9W7n7PtgfJ81ldemrlVr7OAzjCWBJBLh_6ikJKIUR1tTdrZG9fird6bMOlc1yq0yhOzLd7bxPbLHP7ND3phiQ_4KHoGTNaC0z5Z2cKNI_8fQJ-aEhVU</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1628529156</pqid></control><display><type>article</type><title>Fermi Resonance Effects in the Vibrational Spectroscopy of Methyl and Methoxy Groups</title><source>American Chemical Society:Jisc Collections:American Chemical Society Read &amp; Publish Agreement 2022-2024 (Reading list)</source><creator>Sibert, Edwin L ; Tabor, Daniel P ; Kidwell, Nathanael M ; Dean, Jacob C ; Zwier, Timothy S</creator><creatorcontrib>Sibert, Edwin L ; Tabor, Daniel P ; Kidwell, Nathanael M ; Dean, Jacob C ; Zwier, Timothy S</creatorcontrib><description>A theoretical model Hamiltonian [J. Chem. Phys. 2013, 138, 064308] for describing vibrational spectra associated with the CH stretch of CH2 groups is extended to molecules containing methyl and methoxy groups. Results are compared to the infrared (IR) spectroscopy of four molecules studied under supersonic expansion cooling in gas phase conditions. The molecules include 1,1-diphenylethane (DPE), 1,1-diphenylpropane (DPP), 2-methoxyphenol (guaiacol), and 1,3-dimethoxy-2-hydroxybenzene (syringol). Transforming the bending normal mode vibrations of CH3 groups to local scissor vibrations leads to model Hamiltonians which share many features present in our model Hamiltonian for the stretching vibrations of CH2 Fermi coupled to scissor modes. The central difference arises from the greater scissor–scissor coupling present in the CH3 case. Comparing anharmonic couplings between these modes and the stretch–bend Fermi coupling for a variety of systems, it is observed that the anharmonic couplings are robust; their values are similar for the four molecules studied as well as for ethane and methanol. Similar results are obtained with both density functional theory and coupled-cluster calculations. This robustness suggests a new parametrization of the model Hamiltonian that reduces the number of fitting parameters. In contrast, the harmonic contributions to the Hamiltonian vary substantially between the molecules leading to important changes in the spectra. The resulting Hamiltonian predicts most of the major spectral features considered in this study and provides insights into mode mixing and the consequences of the mixing on dynamical processes that follow ultrafast CH stretch excitation.</description><identifier>ISSN: 1089-5639</identifier><identifier>EISSN: 1520-5215</identifier><identifier>DOI: 10.1021/jp510142g</identifier><identifier>PMID: 25373009</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Anharmonicity ; Coupling (molecular) ; Cutting tools ; Mathematical models ; Methyl alcohol ; Spectra ; Spectroscopy ; Vibration</subject><ispartof>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, &amp; general theory, 2014-11, Vol.118 (47), p.11272-11281</ispartof><rights>Copyright © 2014 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a414t-ea32887c421f1bc262addf35834600d922e2f64b6e0201d6c198eac818b27c903</citedby><cites>FETCH-LOGICAL-a414t-ea32887c421f1bc262addf35834600d922e2f64b6e0201d6c198eac818b27c903</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/25373009$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Sibert, Edwin L</creatorcontrib><creatorcontrib>Tabor, Daniel P</creatorcontrib><creatorcontrib>Kidwell, Nathanael M</creatorcontrib><creatorcontrib>Dean, Jacob C</creatorcontrib><creatorcontrib>Zwier, Timothy S</creatorcontrib><title>Fermi Resonance Effects in the Vibrational Spectroscopy of Methyl and Methoxy Groups</title><title>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, &amp; general theory</title><addtitle>J. Phys. Chem. A</addtitle><description>A theoretical model Hamiltonian [J. Chem. Phys. 2013, 138, 064308] for describing vibrational spectra associated with the CH stretch of CH2 groups is extended to molecules containing methyl and methoxy groups. Results are compared to the infrared (IR) spectroscopy of four molecules studied under supersonic expansion cooling in gas phase conditions. The molecules include 1,1-diphenylethane (DPE), 1,1-diphenylpropane (DPP), 2-methoxyphenol (guaiacol), and 1,3-dimethoxy-2-hydroxybenzene (syringol). Transforming the bending normal mode vibrations of CH3 groups to local scissor vibrations leads to model Hamiltonians which share many features present in our model Hamiltonian for the stretching vibrations of CH2 Fermi coupled to scissor modes. The central difference arises from the greater scissor–scissor coupling present in the CH3 case. Comparing anharmonic couplings between these modes and the stretch–bend Fermi coupling for a variety of systems, it is observed that the anharmonic couplings are robust; their values are similar for the four molecules studied as well as for ethane and methanol. Similar results are obtained with both density functional theory and coupled-cluster calculations. This robustness suggests a new parametrization of the model Hamiltonian that reduces the number of fitting parameters. In contrast, the harmonic contributions to the Hamiltonian vary substantially between the molecules leading to important changes in the spectra. The resulting Hamiltonian predicts most of the major spectral features considered in this study and provides insights into mode mixing and the consequences of the mixing on dynamical processes that follow ultrafast CH stretch excitation.</description><subject>Anharmonicity</subject><subject>Coupling (molecular)</subject><subject>Cutting tools</subject><subject>Mathematical models</subject><subject>Methyl alcohol</subject><subject>Spectra</subject><subject>Spectroscopy</subject><subject>Vibration</subject><issn>1089-5639</issn><issn>1520-5215</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2014</creationdate><recordtype>article</recordtype><recordid>eNqFkE1LxDAURYMoOo4u_AOSjaCL6nsvbdouZZhRQRH82pY0TbVD29SkBeffWx2dleDqXbiHC-8wdoRwjkB4sewiBAzpdYtNMCIIIsJoe8yQpEEkRbrH9r1fAgAKCnfZHkUiFgDphD0tjGsq_mC8bVWrDZ-XpdG951XL-zfDX6rcqb4ay5o_dmPjrNe2W3Fb8jvTv61qrtriO9qPFb9yduj8AdspVe3N4c-dsufF_Gl2HdzeX93MLm8DFWLYB0YJSpJYh4Ql5pokqaIoRZSIUAIUKZGhUoa5NECAhdSYJkbpBJOcYp2CmLLT9W7n7PtgfJ81ldemrlVr7OAzjCWBJBLh_6ikJKIUR1tTdrZG9fird6bMOlc1yq0yhOzLd7bxPbLHP7ND3phiQ_4KHoGTNaC0z5Z2cKNI_8fQJ-aEhVU</recordid><startdate>20141126</startdate><enddate>20141126</enddate><creator>Sibert, Edwin L</creator><creator>Tabor, Daniel P</creator><creator>Kidwell, Nathanael M</creator><creator>Dean, Jacob C</creator><creator>Zwier, Timothy S</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope></search><sort><creationdate>20141126</creationdate><title>Fermi Resonance Effects in the Vibrational Spectroscopy of Methyl and Methoxy Groups</title><author>Sibert, Edwin L ; Tabor, Daniel P ; Kidwell, Nathanael M ; Dean, Jacob C ; Zwier, Timothy S</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a414t-ea32887c421f1bc262addf35834600d922e2f64b6e0201d6c198eac818b27c903</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2014</creationdate><topic>Anharmonicity</topic><topic>Coupling (molecular)</topic><topic>Cutting tools</topic><topic>Mathematical models</topic><topic>Methyl alcohol</topic><topic>Spectra</topic><topic>Spectroscopy</topic><topic>Vibration</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Sibert, Edwin L</creatorcontrib><creatorcontrib>Tabor, Daniel P</creatorcontrib><creatorcontrib>Kidwell, Nathanael M</creatorcontrib><creatorcontrib>Dean, Jacob C</creatorcontrib><creatorcontrib>Zwier, Timothy S</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, &amp; general theory</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Sibert, Edwin L</au><au>Tabor, Daniel P</au><au>Kidwell, Nathanael M</au><au>Dean, Jacob C</au><au>Zwier, Timothy S</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Fermi Resonance Effects in the Vibrational Spectroscopy of Methyl and Methoxy Groups</atitle><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, &amp; general theory</jtitle><addtitle>J. Phys. Chem. A</addtitle><date>2014-11-26</date><risdate>2014</risdate><volume>118</volume><issue>47</issue><spage>11272</spage><epage>11281</epage><pages>11272-11281</pages><issn>1089-5639</issn><eissn>1520-5215</eissn><abstract>A theoretical model Hamiltonian [J. Chem. Phys. 2013, 138, 064308] for describing vibrational spectra associated with the CH stretch of CH2 groups is extended to molecules containing methyl and methoxy groups. Results are compared to the infrared (IR) spectroscopy of four molecules studied under supersonic expansion cooling in gas phase conditions. The molecules include 1,1-diphenylethane (DPE), 1,1-diphenylpropane (DPP), 2-methoxyphenol (guaiacol), and 1,3-dimethoxy-2-hydroxybenzene (syringol). Transforming the bending normal mode vibrations of CH3 groups to local scissor vibrations leads to model Hamiltonians which share many features present in our model Hamiltonian for the stretching vibrations of CH2 Fermi coupled to scissor modes. The central difference arises from the greater scissor–scissor coupling present in the CH3 case. Comparing anharmonic couplings between these modes and the stretch–bend Fermi coupling for a variety of systems, it is observed that the anharmonic couplings are robust; their values are similar for the four molecules studied as well as for ethane and methanol. Similar results are obtained with both density functional theory and coupled-cluster calculations. This robustness suggests a new parametrization of the model Hamiltonian that reduces the number of fitting parameters. In contrast, the harmonic contributions to the Hamiltonian vary substantially between the molecules leading to important changes in the spectra. The resulting Hamiltonian predicts most of the major spectral features considered in this study and provides insights into mode mixing and the consequences of the mixing on dynamical processes that follow ultrafast CH stretch excitation.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>25373009</pmid><doi>10.1021/jp510142g</doi><tpages>10</tpages></addata></record>
fulltext fulltext
identifier ISSN: 1089-5639
ispartof The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 2014-11, Vol.118 (47), p.11272-11281
issn 1089-5639
1520-5215
language eng
recordid cdi_proquest_miscellaneous_1762062234
source American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list)
subjects Anharmonicity
Coupling (molecular)
Cutting tools
Mathematical models
Methyl alcohol
Spectra
Spectroscopy
Vibration
title Fermi Resonance Effects in the Vibrational Spectroscopy of Methyl and Methoxy Groups
url http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-23T08%3A18%3A39IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Fermi%20Resonance%20Effects%20in%20the%20Vibrational%20Spectroscopy%20of%20Methyl%20and%20Methoxy%20Groups&rft.jtitle=The%20journal%20of%20physical%20chemistry.%20A,%20Molecules,%20spectroscopy,%20kinetics,%20environment,%20&%20general%20theory&rft.au=Sibert,%20Edwin%20L&rft.date=2014-11-26&rft.volume=118&rft.issue=47&rft.spage=11272&rft.epage=11281&rft.pages=11272-11281&rft.issn=1089-5639&rft.eissn=1520-5215&rft_id=info:doi/10.1021/jp510142g&rft_dat=%3Cproquest_cross%3E1628529156%3C/proquest_cross%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-a414t-ea32887c421f1bc262addf35834600d922e2f64b6e0201d6c198eac818b27c903%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_pqid=1628529156&rft_id=info:pmid/25373009&rfr_iscdi=true