Photodissociation Reaction of 1,2-Diiodoethane in Solution: A Theoretical and X-ray Diffraction Study
Various molecular species are known to form during the photoreaction of C2H4I2 in the gas phase and in solution. We have studied all species involved in this reaction by ab initio and density functional theory (DFT) calculations: Geometries, energies, and vibrational frequencies of C2H4I2, bridged...
Gespeichert in:
Veröffentlicht in: | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2005-11, Vol.109 (45), p.10451-10458 |
---|---|
Hauptverfasser: | , , , , , |
Format: | Artikel |
Sprache: | eng |
Schlagworte: | |
Online-Zugang: | Volltext |
Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
container_end_page | 10458 |
---|---|
container_issue | 45 |
container_start_page | 10451 |
container_title | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory |
container_volume | 109 |
creator | Kong, Qingyu Kim, Joonghan Lorenc, Maciej Kim, Tae Kyu Ihee, Hyotcherl Wulff, Michael |
description | Various molecular species are known to form during the photoreaction of C2H4I2 in the gas phase and in solution. We have studied all species involved in this reaction by ab initio and density functional theory (DFT) calculations: Geometries, energies, and vibrational frequencies of C2H4I2, bridged C2H4I•, anti C2H4I•, C2H4, I2, I3 -, and the isomer C2H4I−I were calculated. The absorption peaks and oscillator strengths of selected species along the potential energy surface (PES) were calculated using time-dependent DFT and were compared with available experimental results. The calculated PES satisfactorily describes the observed reactions of the photoexcited C2H4I2 molecule. In the gas phase, there is only one reaction pathway: the first C−I bond ruptures followed by a secondary C−I breakage in the haloethyl radical C2H4I•. In solution, by contrast, another reaction channel, which is energetically more favored over the secondary dissociation, is switched on due to a solvation effect: the bridged C2H4I• can bind to the free iodine atom to form a C2H4I−I isomer without any energy barrier. The isomer can then break into C2H4 and I2. The rotational barriers in the gas phase and in solution were also calculated and compared. To provide experimental data on the structure of C2H4I2 in solution, the ground state structure of C2H4I2 in methanol was determined from static X-ray diffraction data using 88 keV (λ = 0.14 Å) X-rays. The structural parameters are compared with those from the theoretical results. |
doi_str_mv | 10.1021/jp053390q |
format | Article |
fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_70168907</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>70168907</sourcerecordid><originalsourceid>FETCH-LOGICAL-a417t-75396b451b33b81c52b211eab2571e6f7e60a60c6dfbec4de15b22ac537387c43</originalsourceid><addsrcrecordid>eNptkM1KAzEUhYMotlYXvoBkoyA4mp_JZMZdaf3DgsVW6C5kMhmaOp20yQzYnVtf0ydxakvduLoHzse59x4ATjG6xojgm9kCMUoTtNwDbcwIChjBbL_RKE4CFtGkBY68nyGEMCXhIWjhKKaUhrQNpsOprWxmvLfKyMrYEr5qqX6FzSG-IkHfGJtZXU1lqaEp4cgW9dq__f78gl04nmrrdGWULKAsMzgJnFzBvslzt80ZVXW2OgYHuSy8PtnODni7vxv3HoPBy8NTrzsIZIh5FXBGkygNGU4pTWOsGEkJxlqmhHGso5zrCMkIqSjLU63CTGOWEiIVo5zGXIW0Ay42uQtnl7X2lZgbr3RRNNfb2guOmucTxBvwcgMqZ713OhcLZ-bSrQRGYl2r2NXasGfb0Dqd6-yP3PbYAMEGML7SHztfuncRccqZGA9HYkBHPO49J2LS8OcbXiovZrZ2ZdPJP4t_AKDpjk4</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>70168907</pqid></control><display><type>article</type><title>Photodissociation Reaction of 1,2-Diiodoethane in Solution: A Theoretical and X-ray Diffraction Study</title><source>MEDLINE</source><source>American Chemical Society Journals</source><creator>Kong, Qingyu ; Kim, Joonghan ; Lorenc, Maciej ; Kim, Tae Kyu ; Ihee, Hyotcherl ; Wulff, Michael</creator><creatorcontrib>Kong, Qingyu ; Kim, Joonghan ; Lorenc, Maciej ; Kim, Tae Kyu ; Ihee, Hyotcherl ; Wulff, Michael</creatorcontrib><description>Various molecular species are known to form during the photoreaction of C2H4I2 in the gas phase and in solution. We have studied all species involved in this reaction by ab initio and density functional theory (DFT) calculations: Geometries, energies, and vibrational frequencies of C2H4I2, bridged C2H4I•, anti C2H4I•, C2H4, I2, I3 -, and the isomer C2H4I−I were calculated. The absorption peaks and oscillator strengths of selected species along the potential energy surface (PES) were calculated using time-dependent DFT and were compared with available experimental results. The calculated PES satisfactorily describes the observed reactions of the photoexcited C2H4I2 molecule. In the gas phase, there is only one reaction pathway: the first C−I bond ruptures followed by a secondary C−I breakage in the haloethyl radical C2H4I•. In solution, by contrast, another reaction channel, which is energetically more favored over the secondary dissociation, is switched on due to a solvation effect: the bridged C2H4I• can bind to the free iodine atom to form a C2H4I−I isomer without any energy barrier. The isomer can then break into C2H4 and I2. The rotational barriers in the gas phase and in solution were also calculated and compared. To provide experimental data on the structure of C2H4I2 in solution, the ground state structure of C2H4I2 in methanol was determined from static X-ray diffraction data using 88 keV (λ = 0.14 Å) X-rays. The structural parameters are compared with those from the theoretical results.</description><identifier>ISSN: 1089-5639</identifier><identifier>EISSN: 1520-5215</identifier><identifier>DOI: 10.1021/jp053390q</identifier><identifier>PMID: 16833343</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Computer Simulation ; Hydrocarbons, Iodinated - chemistry ; Models, Chemical ; Photochemistry ; Quantum Theory ; Solutions - chemistry ; X-Ray Diffraction</subject><ispartof>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 2005-11, Vol.109 (45), p.10451-10458</ispartof><rights>Copyright © 2005 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a417t-75396b451b33b81c52b211eab2571e6f7e60a60c6dfbec4de15b22ac537387c43</citedby><cites>FETCH-LOGICAL-a417t-75396b451b33b81c52b211eab2571e6f7e60a60c6dfbec4de15b22ac537387c43</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jp053390q$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jp053390q$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/16833343$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Kong, Qingyu</creatorcontrib><creatorcontrib>Kim, Joonghan</creatorcontrib><creatorcontrib>Lorenc, Maciej</creatorcontrib><creatorcontrib>Kim, Tae Kyu</creatorcontrib><creatorcontrib>Ihee, Hyotcherl</creatorcontrib><creatorcontrib>Wulff, Michael</creatorcontrib><title>Photodissociation Reaction of 1,2-Diiodoethane in Solution: A Theoretical and X-ray Diffraction Study</title><title>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</title><addtitle>J. Phys. Chem. A</addtitle><description>Various molecular species are known to form during the photoreaction of C2H4I2 in the gas phase and in solution. We have studied all species involved in this reaction by ab initio and density functional theory (DFT) calculations: Geometries, energies, and vibrational frequencies of C2H4I2, bridged C2H4I•, anti C2H4I•, C2H4, I2, I3 -, and the isomer C2H4I−I were calculated. The absorption peaks and oscillator strengths of selected species along the potential energy surface (PES) were calculated using time-dependent DFT and were compared with available experimental results. The calculated PES satisfactorily describes the observed reactions of the photoexcited C2H4I2 molecule. In the gas phase, there is only one reaction pathway: the first C−I bond ruptures followed by a secondary C−I breakage in the haloethyl radical C2H4I•. In solution, by contrast, another reaction channel, which is energetically more favored over the secondary dissociation, is switched on due to a solvation effect: the bridged C2H4I• can bind to the free iodine atom to form a C2H4I−I isomer without any energy barrier. The isomer can then break into C2H4 and I2. The rotational barriers in the gas phase and in solution were also calculated and compared. To provide experimental data on the structure of C2H4I2 in solution, the ground state structure of C2H4I2 in methanol was determined from static X-ray diffraction data using 88 keV (λ = 0.14 Å) X-rays. The structural parameters are compared with those from the theoretical results.</description><subject>Computer Simulation</subject><subject>Hydrocarbons, Iodinated - chemistry</subject><subject>Models, Chemical</subject><subject>Photochemistry</subject><subject>Quantum Theory</subject><subject>Solutions - chemistry</subject><subject>X-Ray Diffraction</subject><issn>1089-5639</issn><issn>1520-5215</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2005</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkM1KAzEUhYMotlYXvoBkoyA4mp_JZMZdaf3DgsVW6C5kMhmaOp20yQzYnVtf0ydxakvduLoHzse59x4ATjG6xojgm9kCMUoTtNwDbcwIChjBbL_RKE4CFtGkBY68nyGEMCXhIWjhKKaUhrQNpsOprWxmvLfKyMrYEr5qqX6FzSG-IkHfGJtZXU1lqaEp4cgW9dq__f78gl04nmrrdGWULKAsMzgJnFzBvslzt80ZVXW2OgYHuSy8PtnODni7vxv3HoPBy8NTrzsIZIh5FXBGkygNGU4pTWOsGEkJxlqmhHGso5zrCMkIqSjLU63CTGOWEiIVo5zGXIW0Ay42uQtnl7X2lZgbr3RRNNfb2guOmucTxBvwcgMqZ713OhcLZ-bSrQRGYl2r2NXasGfb0Dqd6-yP3PbYAMEGML7SHztfuncRccqZGA9HYkBHPO49J2LS8OcbXiovZrZ2ZdPJP4t_AKDpjk4</recordid><startdate>20051117</startdate><enddate>20051117</enddate><creator>Kong, Qingyu</creator><creator>Kim, Joonghan</creator><creator>Lorenc, Maciej</creator><creator>Kim, Tae Kyu</creator><creator>Ihee, Hyotcherl</creator><creator>Wulff, Michael</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20051117</creationdate><title>Photodissociation Reaction of 1,2-Diiodoethane in Solution: A Theoretical and X-ray Diffraction Study</title><author>Kong, Qingyu ; Kim, Joonghan ; Lorenc, Maciej ; Kim, Tae Kyu ; Ihee, Hyotcherl ; Wulff, Michael</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a417t-75396b451b33b81c52b211eab2571e6f7e60a60c6dfbec4de15b22ac537387c43</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2005</creationdate><topic>Computer Simulation</topic><topic>Hydrocarbons, Iodinated - chemistry</topic><topic>Models, Chemical</topic><topic>Photochemistry</topic><topic>Quantum Theory</topic><topic>Solutions - chemistry</topic><topic>X-Ray Diffraction</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kong, Qingyu</creatorcontrib><creatorcontrib>Kim, Joonghan</creatorcontrib><creatorcontrib>Lorenc, Maciej</creatorcontrib><creatorcontrib>Kim, Tae Kyu</creatorcontrib><creatorcontrib>Ihee, Hyotcherl</creatorcontrib><creatorcontrib>Wulff, Michael</creatorcontrib><collection>Istex</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kong, Qingyu</au><au>Kim, Joonghan</au><au>Lorenc, Maciej</au><au>Kim, Tae Kyu</au><au>Ihee, Hyotcherl</au><au>Wulff, Michael</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Photodissociation Reaction of 1,2-Diiodoethane in Solution: A Theoretical and X-ray Diffraction Study</atitle><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</jtitle><addtitle>J. Phys. Chem. A</addtitle><date>2005-11-17</date><risdate>2005</risdate><volume>109</volume><issue>45</issue><spage>10451</spage><epage>10458</epage><pages>10451-10458</pages><issn>1089-5639</issn><eissn>1520-5215</eissn><abstract>Various molecular species are known to form during the photoreaction of C2H4I2 in the gas phase and in solution. We have studied all species involved in this reaction by ab initio and density functional theory (DFT) calculations: Geometries, energies, and vibrational frequencies of C2H4I2, bridged C2H4I•, anti C2H4I•, C2H4, I2, I3 -, and the isomer C2H4I−I were calculated. The absorption peaks and oscillator strengths of selected species along the potential energy surface (PES) were calculated using time-dependent DFT and were compared with available experimental results. The calculated PES satisfactorily describes the observed reactions of the photoexcited C2H4I2 molecule. In the gas phase, there is only one reaction pathway: the first C−I bond ruptures followed by a secondary C−I breakage in the haloethyl radical C2H4I•. In solution, by contrast, another reaction channel, which is energetically more favored over the secondary dissociation, is switched on due to a solvation effect: the bridged C2H4I• can bind to the free iodine atom to form a C2H4I−I isomer without any energy barrier. The isomer can then break into C2H4 and I2. The rotational barriers in the gas phase and in solution were also calculated and compared. To provide experimental data on the structure of C2H4I2 in solution, the ground state structure of C2H4I2 in methanol was determined from static X-ray diffraction data using 88 keV (λ = 0.14 Å) X-rays. The structural parameters are compared with those from the theoretical results.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>16833343</pmid><doi>10.1021/jp053390q</doi><tpages>8</tpages></addata></record> |
fulltext | fulltext |
identifier | ISSN: 1089-5639 |
ispartof | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 2005-11, Vol.109 (45), p.10451-10458 |
issn | 1089-5639 1520-5215 |
language | eng |
recordid | cdi_proquest_miscellaneous_70168907 |
source | MEDLINE; American Chemical Society Journals |
subjects | Computer Simulation Hydrocarbons, Iodinated - chemistry Models, Chemical Photochemistry Quantum Theory Solutions - chemistry X-Ray Diffraction |
title | Photodissociation Reaction of 1,2-Diiodoethane in Solution: A Theoretical and X-ray Diffraction Study |
url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-25T11%3A22%3A59IST&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=Photodissociation%20Reaction%20of%201,2-Diiodoethane%20in%20Solution:%E2%80%89%20A%20Theoretical%20and%20X-ray%20Diffraction%20Study&rft.jtitle=The%20journal%20of%20physical%20chemistry.%20A,%20Molecules,%20spectroscopy,%20kinetics,%20environment,%20&%20general%20theory&rft.au=Kong,%20Qingyu&rft.date=2005-11-17&rft.volume=109&rft.issue=45&rft.spage=10451&rft.epage=10458&rft.pages=10451-10458&rft.issn=1089-5639&rft.eissn=1520-5215&rft_id=info:doi/10.1021/jp053390q&rft_dat=%3Cproquest_cross%3E70168907%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=70168907&rft_id=info:pmid/16833343&rfr_iscdi=true |