Density-functional errors in ionization potential with increasing system size
This work investigates the effects of molecular size on the accuracy of density-functional ionization potentials for a set of 28 hydrocarbons, including series of alkanes, alkenes, and oligoacenes. As the system size increases, delocalization error introduces a systematic underestimation of the ioni...
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| Veröffentlicht in: | The Journal of chemical physics 2015-05, Vol.142 (18), p.184106-184106 |
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| container_end_page | 184106 |
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| container_issue | 18 |
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| container_title | The Journal of chemical physics |
| container_volume | 142 |
| creator | Whittleton, Sarah R. Sosa Vazquez, Xochitl A. Isborn, Christine M. Johnson, Erin R. |
| description | This work investigates the effects of molecular size on the accuracy of density-functional ionization potentials for a set of 28 hydrocarbons, including series of alkanes, alkenes, and oligoacenes. As the system size increases, delocalization error introduces a systematic underestimation of the ionization potential, which is rationalized by considering the fractional-charge behavior of the electronic energies. The computation of the ionization potential with many density-functional approximations is not size-extensive due to excessive delocalization of the incipient positive charge. While inclusion of exact exchange reduces the observed errors, system-specific tuning of long-range corrected functionals does not generally improve accuracy. These results emphasize that good performance of a functional for small molecules is not necessarily transferable to larger systems. |
| doi_str_mv | 10.1063/1.4920947 |
| format | Article |
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As the system size increases, delocalization error introduces a systematic underestimation of the ionization potential, which is rationalized by considering the fractional-charge behavior of the electronic energies. The computation of the ionization potential with many density-functional approximations is not size-extensive due to excessive delocalization of the incipient positive charge. While inclusion of exact exchange reduces the observed errors, system-specific tuning of long-range corrected functionals does not generally improve accuracy. 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As the system size increases, delocalization error introduces a systematic underestimation of the ionization potential, which is rationalized by considering the fractional-charge behavior of the electronic energies. The computation of the ionization potential with many density-functional approximations is not size-extensive due to excessive delocalization of the incipient positive charge. While inclusion of exact exchange reduces the observed errors, system-specific tuning of long-range corrected functionals does not generally improve accuracy. These results emphasize that good performance of a functional for small molecules is not necessarily transferable to larger systems.</description><subject>ALKANES</subject><subject>ALKENES</subject><subject>Density</subject><subject>DENSITY FUNCTIONAL METHOD</subject><subject>FUNCTIONALS</subject><subject>Hydrocarbons</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>IONIZATION POTENTIAL</subject><subject>Ionization potentials</subject><subject>MOLECULES</subject><subject>POTENTIALS</subject><issn>0021-9606</issn><issn>1089-7690</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><recordid>eNp90c9vVCEQB3BibOxaPfgPmJd4UZNXGeAB72jqryY1XvRMgB0szS6swNNs__q-ddftoYknAvPJl8kMIS-AngOV_B2ci5HRUahHZAFUj72SI31MFpQy6EdJ5Sl5WusNpRQUE0_IKRtGpbVmC_L1A6Ya27YPU_It5mRXHZaSS-1i6uZ7vLW7526TG6YW5_Kf2K7noi9oa0w_u7qtDdddjbf4jJwEu6r4_HCekR-fPn6_-NJffft8efH-qvcCoPUuiHFA8EoIJQe-lIN02iH1KALjjFmggjoMIKRFycOSWu94AGXBOcctPyOv9rm5tmiqjw39tc8poW-GMQGDkmxWr_dqU_KvCWsz61g9rlY2YZ6qAalhBFCjvg880ps8lXkY1TCqNZd0GPis3uyVL7nWgsFsSlzbsjVAzW4TBsxhE7N9eUic3BqXR_lv9DN4uwe79v_O-Gh-53KfZDbL8D_88Os729ye5w</recordid><startdate>20150514</startdate><enddate>20150514</enddate><creator>Whittleton, Sarah R.</creator><creator>Sosa Vazquez, Xochitl A.</creator><creator>Isborn, Christine M.</creator><creator>Johnson, Erin R.</creator><general>American Institute of Physics</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>8FD</scope><scope>H8D</scope><scope>L7M</scope><scope>7X8</scope><scope>OTOTI</scope></search><sort><creationdate>20150514</creationdate><title>Density-functional errors in ionization potential with increasing system size</title><author>Whittleton, Sarah R. ; Sosa Vazquez, Xochitl A. ; Isborn, Christine M. ; Johnson, Erin R.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c411t-bf495e1c7447653d656b8be0ce4f2322a1040bef146ae63fd0acb3f17a1bbb3a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>ALKANES</topic><topic>ALKENES</topic><topic>Density</topic><topic>DENSITY FUNCTIONAL METHOD</topic><topic>FUNCTIONALS</topic><topic>Hydrocarbons</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>IONIZATION POTENTIAL</topic><topic>Ionization potentials</topic><topic>MOLECULES</topic><topic>POTENTIALS</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Whittleton, Sarah R.</creatorcontrib><creatorcontrib>Sosa Vazquez, Xochitl A.</creatorcontrib><creatorcontrib>Isborn, Christine M.</creatorcontrib><creatorcontrib>Johnson, Erin R.</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Technology Research Database</collection><collection>Aerospace Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><collection>OSTI.GOV</collection><jtitle>The Journal of chemical physics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Whittleton, Sarah R.</au><au>Sosa Vazquez, Xochitl A.</au><au>Isborn, Christine M.</au><au>Johnson, Erin R.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Density-functional errors in ionization potential with increasing system size</atitle><jtitle>The Journal of chemical physics</jtitle><addtitle>J Chem Phys</addtitle><date>2015-05-14</date><risdate>2015</risdate><volume>142</volume><issue>18</issue><spage>184106</spage><epage>184106</epage><pages>184106-184106</pages><issn>0021-9606</issn><eissn>1089-7690</eissn><coden>JCPSA6</coden><abstract>This work investigates the effects of molecular size on the accuracy of density-functional ionization potentials for a set of 28 hydrocarbons, including series of alkanes, alkenes, and oligoacenes. 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| ispartof | The Journal of chemical physics, 2015-05, Vol.142 (18), p.184106-184106 |
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| language | eng |
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| source | American Institute of Physics (AIP) Journals; Alma/SFX Local Collection |
| subjects | ALKANES ALKENES Density DENSITY FUNCTIONAL METHOD FUNCTIONALS Hydrocarbons INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY IONIZATION POTENTIAL Ionization potentials MOLECULES POTENTIALS |
| title | Density-functional errors in ionization potential with increasing system size |
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