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Photoelectron spectroscopy of CH2N
We have measured the negative ion photoelectron spectra of CH2N− and CD2N− and find the electron affinities: EA(CH2N)=0.511±0.008 eV and EA(CD2N)=0.498±0.011 eV. Franck–Condon simulations of these spectra are carried out and we estimate the CH2N− and CH2N geometry differences; we fit our spectra wit...
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Published in: | The Journal of chemical physics 1991-03, Vol.94 (5), p.3517-3528 |
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container_end_page | 3528 |
container_issue | 5 |
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container_title | The Journal of chemical physics |
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creator | COWLES, D. C TRAVERS, M. J FRUEH, J. L ELLISON, G. B |
description | We have measured the negative ion photoelectron spectra of CH2N− and CD2N− and find the electron affinities: EA(CH2N)=0.511±0.008 eV and EA(CD2N)=0.498±0.011 eV. Franck–Condon simulations of these spectra are carried out and we estimate the CH2N− and CH2N geometry differences; we fit our spectra with the following [constrained] molecular structures. We combine our EA(CH2N) with the results of previous gas phase ion studies to extract a number of thermochemical parameters (kcal/mol): Do0(CH2N–H)=85±5, Do0(H–HCN)=23±6, Do0(H2C–N)=144±6, and the isomerization enthalpy of H2CN+→HCNH+ is ΔHisom(C2v→C∞v)=−51±7. Attempts to calculate the geometry and vibrational frequencies of the H2CN radical are disappointing. Unrestricted Hartree–Fock and second-order Mo/ller–Plesset ab initio calculations in a 6-31++G** basis produce badly spin-contaminated wave functions which do not reproduce the experimental findings. |
doi_str_mv | 10.1063/1.459773 |
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B</creator><creatorcontrib>COWLES, D. C ; TRAVERS, M. J ; FRUEH, J. L ; ELLISON, G. B</creatorcontrib><description>We have measured the negative ion photoelectron spectra of CH2N− and CD2N− and find the electron affinities: EA(CH2N)=0.511±0.008 eV and EA(CD2N)=0.498±0.011 eV. Franck–Condon simulations of these spectra are carried out and we estimate the CH2N− and CH2N geometry differences; we fit our spectra with the following [constrained] molecular structures. We combine our EA(CH2N) with the results of previous gas phase ion studies to extract a number of thermochemical parameters (kcal/mol): Do0(CH2N–H)=85±5, Do0(H–HCN)=23±6, Do0(H2C–N)=144±6, and the isomerization enthalpy of H2CN+→HCNH+ is ΔHisom(C2v→C∞v)=−51±7. Attempts to calculate the geometry and vibrational frequencies of the H2CN radical are disappointing. Unrestricted Hartree–Fock and second-order Mo/ller–Plesset ab initio calculations in a 6-31++G** basis produce badly spin-contaminated wave functions which do not reproduce the experimental findings.</description><identifier>ISSN: 0021-9606</identifier><identifier>EISSN: 1089-7690</identifier><identifier>DOI: 10.1063/1.459773</identifier><identifier>CODEN: JCPSA6</identifier><language>eng</language><publisher>Woodbury, NY: American Institute of Physics</publisher><subject>Atomic and molecular physics ; Exact sciences and technology ; Molecular properties and interactions with photons ; Photoelectron spectra ; Physics</subject><ispartof>The Journal of chemical physics, 1991-03, Vol.94 (5), p.3517-3528</ispartof><rights>1991 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c257t-558063bcf60ebb8b291cfd3d05c7a83ea8f780c52bc0a613dcbdbd6e6fe0a06d3</citedby><cites>FETCH-LOGICAL-c257t-558063bcf60ebb8b291cfd3d05c7a83ea8f780c52bc0a613dcbdbd6e6fe0a06d3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,782,784,27924,27925</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=19704528$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>COWLES, D. C</creatorcontrib><creatorcontrib>TRAVERS, M. J</creatorcontrib><creatorcontrib>FRUEH, J. L</creatorcontrib><creatorcontrib>ELLISON, G. B</creatorcontrib><title>Photoelectron spectroscopy of CH2N</title><title>The Journal of chemical physics</title><description>We have measured the negative ion photoelectron spectra of CH2N− and CD2N− and find the electron affinities: EA(CH2N)=0.511±0.008 eV and EA(CD2N)=0.498±0.011 eV. Franck–Condon simulations of these spectra are carried out and we estimate the CH2N− and CH2N geometry differences; we fit our spectra with the following [constrained] molecular structures. We combine our EA(CH2N) with the results of previous gas phase ion studies to extract a number of thermochemical parameters (kcal/mol): Do0(CH2N–H)=85±5, Do0(H–HCN)=23±6, Do0(H2C–N)=144±6, and the isomerization enthalpy of H2CN+→HCNH+ is ΔHisom(C2v→C∞v)=−51±7. Attempts to calculate the geometry and vibrational frequencies of the H2CN radical are disappointing. Unrestricted Hartree–Fock and second-order Mo/ller–Plesset ab initio calculations in a 6-31++G** basis produce badly spin-contaminated wave functions which do not reproduce the experimental findings.</description><subject>Atomic and molecular physics</subject><subject>Exact sciences and technology</subject><subject>Molecular properties and interactions with photons</subject><subject>Photoelectron spectra</subject><subject>Physics</subject><issn>0021-9606</issn><issn>1089-7690</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1991</creationdate><recordtype>article</recordtype><recordid>eNpFj0tLxDAUhYMoWEfBn1AEwU3Hm6R5LaWoIwzqQtchuUlwpE5K0838e6sVXJ2z-DgPQi4prClIfkvXrTBK8SNSUdCmUdLAMakAGG2MBHlKzkr5BACqWFuRq9ePPOXYR5zGvK_L8GsK5uFQ51R3G_Z8Tk6S60u8-NMVeX-4f-s2zfbl8am72zbIhJoaIfTc7zFJiN5rzwzFFHgAgcppHp1OSgMK5hGcpDygDz7IKFMEBzLwFblZcnEeUMaY7DDuvtx4sBTszzdL7fJtRq8XdHAFXZ9Gt8dd-eeNglYwzb8BH6tNNg</recordid><startdate>19910301</startdate><enddate>19910301</enddate><creator>COWLES, D. C</creator><creator>TRAVERS, M. J</creator><creator>FRUEH, J. L</creator><creator>ELLISON, G. B</creator><general>American Institute of Physics</general><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>19910301</creationdate><title>Photoelectron spectroscopy of CH2N</title><author>COWLES, D. C ; TRAVERS, M. J ; FRUEH, J. L ; ELLISON, G. B</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c257t-558063bcf60ebb8b291cfd3d05c7a83ea8f780c52bc0a613dcbdbd6e6fe0a06d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1991</creationdate><topic>Atomic and molecular physics</topic><topic>Exact sciences and technology</topic><topic>Molecular properties and interactions with photons</topic><topic>Photoelectron spectra</topic><topic>Physics</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>COWLES, D. C</creatorcontrib><creatorcontrib>TRAVERS, M. J</creatorcontrib><creatorcontrib>FRUEH, J. L</creatorcontrib><creatorcontrib>ELLISON, G. B</creatorcontrib><collection>Pascal-Francis</collection><collection>CrossRef</collection><jtitle>The Journal of chemical physics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>COWLES, D. C</au><au>TRAVERS, M. J</au><au>FRUEH, J. L</au><au>ELLISON, G. B</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Photoelectron spectroscopy of CH2N</atitle><jtitle>The Journal of chemical physics</jtitle><date>1991-03-01</date><risdate>1991</risdate><volume>94</volume><issue>5</issue><spage>3517</spage><epage>3528</epage><pages>3517-3528</pages><issn>0021-9606</issn><eissn>1089-7690</eissn><coden>JCPSA6</coden><abstract>We have measured the negative ion photoelectron spectra of CH2N− and CD2N− and find the electron affinities: EA(CH2N)=0.511±0.008 eV and EA(CD2N)=0.498±0.011 eV. Franck–Condon simulations of these spectra are carried out and we estimate the CH2N− and CH2N geometry differences; we fit our spectra with the following [constrained] molecular structures. We combine our EA(CH2N) with the results of previous gas phase ion studies to extract a number of thermochemical parameters (kcal/mol): Do0(CH2N–H)=85±5, Do0(H–HCN)=23±6, Do0(H2C–N)=144±6, and the isomerization enthalpy of H2CN+→HCNH+ is ΔHisom(C2v→C∞v)=−51±7. Attempts to calculate the geometry and vibrational frequencies of the H2CN radical are disappointing. Unrestricted Hartree–Fock and second-order Mo/ller–Plesset ab initio calculations in a 6-31++G** basis produce badly spin-contaminated wave functions which do not reproduce the experimental findings.</abstract><cop>Woodbury, NY</cop><pub>American Institute of Physics</pub><doi>10.1063/1.459773</doi><tpages>12</tpages></addata></record> |
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source | AIP_美国物理联合会现刊(与NSTL共建) |
subjects | Atomic and molecular physics Exact sciences and technology Molecular properties and interactions with photons Photoelectron spectra Physics |
title | Photoelectron spectroscopy of CH2N |
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