Origin of the success of mGGAs for bandgaps

One of the well-known limitations of Kohn–Sham density functional theory is the tendency to strongly underestimate bandgaps. Meta-generalized gradient approximations (mGGAs), which include the kinetic energy density in the functional form, have been shown to significantly alleviate this deficiency....

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:The Journal of chemical physics 2023-12, Vol.159 (24)
Hauptverfasser: Kovács, Péter, Blaha, Peter, Madsen, Georg K. H.
Format: Artikel
Sprache:eng
Schlagworte:
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page
container_issue 24
container_start_page
container_title The Journal of chemical physics
container_volume 159
creator Kovács, Péter
Blaha, Peter
Madsen, Georg K. H.
description One of the well-known limitations of Kohn–Sham density functional theory is the tendency to strongly underestimate bandgaps. Meta-generalized gradient approximations (mGGAs), which include the kinetic energy density in the functional form, have been shown to significantly alleviate this deficiency. In this study, we explore the mechanisms responsible for this improvement from the angle of the underlying local densities. We find that the highest occupied and lowest unoccupied states are distinct in the space of the underlying descriptors. The gap opening is compared to a simple scaling of the local density approximation, and two mechanisms responsible for opening the mGGA gaps are identified. First of all, the relatively large negative derivative of the functional form with respect to reduced kinetic energy tends to elevate the lowest unoccupied state. Second, the curvature of functional, which ensures that it is bounded, tends to lower the highest occupied state. Remarkably, these two mechanisms are found to be transferable over a large and diverse database of compounds.
doi_str_mv 10.1063/5.0179260
format Article
fullrecord <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_crossref_primary_10_1063_5_0179260</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2909084622</sourcerecordid><originalsourceid>FETCH-LOGICAL-c383t-a60b86c0e508d6f996a84dcdf3b947ba38072d2aefc3d827997b51db67b6ed83</originalsourceid><addsrcrecordid>eNp90EtLw0AUBeBBFFurC_-ABNz4IPXOI_NYlqJVKHTTfZhXakqT1Jlk4b9vQqsLF64uFz4Oh4PQLYYpBk5fsilgoQiHMzTGIFUquIJzNAYgOFUc-AhdxbgF6Blhl2hEJc44p2yMnleh3JR10hRJ--mT2FnrYxzearGYxaRoQmJ07TZ6H6_RRaF30d-c7gSt317X8_d0uVp8zGfL1FJJ21RzMJJb8BlIxwuluJbMWVdQo5gwmkoQxBHtC0udJEIpYTLsDBeGeyfpBD0cY_eh-ep8bPOqjNbvdrr2TRdzokCBZJyQnt7_odumC3VfblAiY5yxQT0elQ1NjMEX-T6UlQ7fOYZ8GDDP8tOAvb07JXam8u5X_izWg6cjiLZsdVs29T9pBxlCdN8</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2907546442</pqid></control><display><type>article</type><title>Origin of the success of mGGAs for bandgaps</title><source>AIP Journals Complete</source><source>Alma/SFX Local Collection</source><creator>Kovács, Péter ; Blaha, Peter ; Madsen, Georg K. H.</creator><creatorcontrib>Kovács, Péter ; Blaha, Peter ; Madsen, Georg K. H.</creatorcontrib><description>One of the well-known limitations of Kohn–Sham density functional theory is the tendency to strongly underestimate bandgaps. Meta-generalized gradient approximations (mGGAs), which include the kinetic energy density in the functional form, have been shown to significantly alleviate this deficiency. In this study, we explore the mechanisms responsible for this improvement from the angle of the underlying local densities. We find that the highest occupied and lowest unoccupied states are distinct in the space of the underlying descriptors. The gap opening is compared to a simple scaling of the local density approximation, and two mechanisms responsible for opening the mGGA gaps are identified. First of all, the relatively large negative derivative of the functional form with respect to reduced kinetic energy tends to elevate the lowest unoccupied state. Second, the curvature of functional, which ensures that it is bounded, tends to lower the highest occupied state. Remarkably, these two mechanisms are found to be transferable over a large and diverse database of compounds.</description><identifier>ISSN: 0021-9606</identifier><identifier>EISSN: 1089-7690</identifier><identifier>DOI: 10.1063/5.0179260</identifier><identifier>PMID: 38156634</identifier><identifier>CODEN: JCPSA6</identifier><language>eng</language><publisher>United States: American Institute of Physics</publisher><subject>Approximation ; Density functional theory ; Energy gap ; Kinetic energy ; Physics</subject><ispartof>The Journal of chemical physics, 2023-12, Vol.159 (24)</ispartof><rights>Author(s)</rights><rights>2023 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c383t-a60b86c0e508d6f996a84dcdf3b947ba38072d2aefc3d827997b51db67b6ed83</citedby><cites>FETCH-LOGICAL-c383t-a60b86c0e508d6f996a84dcdf3b947ba38072d2aefc3d827997b51db67b6ed83</cites><orcidid>0000-0001-9844-9145 ; 0000-0001-5849-5788</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://pubs.aip.org/jcp/article-lookup/doi/10.1063/5.0179260$$EHTML$$P50$$Gscitation$$Hfree_for_read</linktohtml><link.rule.ids>314,776,780,790,4498,27903,27904,76130</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/38156634$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Kovács, Péter</creatorcontrib><creatorcontrib>Blaha, Peter</creatorcontrib><creatorcontrib>Madsen, Georg K. H.</creatorcontrib><title>Origin of the success of mGGAs for bandgaps</title><title>The Journal of chemical physics</title><addtitle>J Chem Phys</addtitle><description>One of the well-known limitations of Kohn–Sham density functional theory is the tendency to strongly underestimate bandgaps. Meta-generalized gradient approximations (mGGAs), which include the kinetic energy density in the functional form, have been shown to significantly alleviate this deficiency. In this study, we explore the mechanisms responsible for this improvement from the angle of the underlying local densities. We find that the highest occupied and lowest unoccupied states are distinct in the space of the underlying descriptors. The gap opening is compared to a simple scaling of the local density approximation, and two mechanisms responsible for opening the mGGA gaps are identified. First of all, the relatively large negative derivative of the functional form with respect to reduced kinetic energy tends to elevate the lowest unoccupied state. Second, the curvature of functional, which ensures that it is bounded, tends to lower the highest occupied state. Remarkably, these two mechanisms are found to be transferable over a large and diverse database of compounds.</description><subject>Approximation</subject><subject>Density functional theory</subject><subject>Energy gap</subject><subject>Kinetic energy</subject><subject>Physics</subject><issn>0021-9606</issn><issn>1089-7690</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNp90EtLw0AUBeBBFFurC_-ABNz4IPXOI_NYlqJVKHTTfZhXakqT1Jlk4b9vQqsLF64uFz4Oh4PQLYYpBk5fsilgoQiHMzTGIFUquIJzNAYgOFUc-AhdxbgF6Blhl2hEJc44p2yMnleh3JR10hRJ--mT2FnrYxzearGYxaRoQmJ07TZ6H6_RRaF30d-c7gSt317X8_d0uVp8zGfL1FJJ21RzMJJb8BlIxwuluJbMWVdQo5gwmkoQxBHtC0udJEIpYTLsDBeGeyfpBD0cY_eh-ep8bPOqjNbvdrr2TRdzokCBZJyQnt7_odumC3VfblAiY5yxQT0elQ1NjMEX-T6UlQ7fOYZ8GDDP8tOAvb07JXam8u5X_izWg6cjiLZsdVs29T9pBxlCdN8</recordid><startdate>20231228</startdate><enddate>20231228</enddate><creator>Kovács, Péter</creator><creator>Blaha, Peter</creator><creator>Madsen, Georg K. H.</creator><general>American Institute of Physics</general><scope>AJDQP</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>8FD</scope><scope>H8D</scope><scope>L7M</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0001-9844-9145</orcidid><orcidid>https://orcid.org/0000-0001-5849-5788</orcidid></search><sort><creationdate>20231228</creationdate><title>Origin of the success of mGGAs for bandgaps</title><author>Kovács, Péter ; Blaha, Peter ; Madsen, Georg K. H.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c383t-a60b86c0e508d6f996a84dcdf3b947ba38072d2aefc3d827997b51db67b6ed83</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>Approximation</topic><topic>Density functional theory</topic><topic>Energy gap</topic><topic>Kinetic energy</topic><topic>Physics</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kovács, Péter</creatorcontrib><creatorcontrib>Blaha, Peter</creatorcontrib><creatorcontrib>Madsen, Georg K. H.</creatorcontrib><collection>AIP Open Access Journals</collection><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><jtitle>The Journal of chemical physics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kovács, Péter</au><au>Blaha, Peter</au><au>Madsen, Georg K. H.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Origin of the success of mGGAs for bandgaps</atitle><jtitle>The Journal of chemical physics</jtitle><addtitle>J Chem Phys</addtitle><date>2023-12-28</date><risdate>2023</risdate><volume>159</volume><issue>24</issue><issn>0021-9606</issn><eissn>1089-7690</eissn><coden>JCPSA6</coden><abstract>One of the well-known limitations of Kohn–Sham density functional theory is the tendency to strongly underestimate bandgaps. Meta-generalized gradient approximations (mGGAs), which include the kinetic energy density in the functional form, have been shown to significantly alleviate this deficiency. In this study, we explore the mechanisms responsible for this improvement from the angle of the underlying local densities. We find that the highest occupied and lowest unoccupied states are distinct in the space of the underlying descriptors. The gap opening is compared to a simple scaling of the local density approximation, and two mechanisms responsible for opening the mGGA gaps are identified. First of all, the relatively large negative derivative of the functional form with respect to reduced kinetic energy tends to elevate the lowest unoccupied state. Second, the curvature of functional, which ensures that it is bounded, tends to lower the highest occupied state. Remarkably, these two mechanisms are found to be transferable over a large and diverse database of compounds.</abstract><cop>United States</cop><pub>American Institute of Physics</pub><pmid>38156634</pmid><doi>10.1063/5.0179260</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0001-9844-9145</orcidid><orcidid>https://orcid.org/0000-0001-5849-5788</orcidid><oa>free_for_read</oa></addata></record>
fulltext fulltext
identifier ISSN: 0021-9606
ispartof The Journal of chemical physics, 2023-12, Vol.159 (24)
issn 0021-9606
1089-7690
language eng
recordid cdi_crossref_primary_10_1063_5_0179260
source AIP Journals Complete; Alma/SFX Local Collection
subjects Approximation
Density functional theory
Energy gap
Kinetic energy
Physics
title Origin of the success of mGGAs for bandgaps
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-27T14%3A45%3A37IST&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=Origin%20of%20the%20success%20of%20mGGAs%20for%20bandgaps&rft.jtitle=The%20Journal%20of%20chemical%20physics&rft.au=Kov%C3%A1cs,%20P%C3%A9ter&rft.date=2023-12-28&rft.volume=159&rft.issue=24&rft.issn=0021-9606&rft.eissn=1089-7690&rft.coden=JCPSA6&rft_id=info:doi/10.1063/5.0179260&rft_dat=%3Cproquest_cross%3E2909084622%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=2907546442&rft_id=info:pmid/38156634&rfr_iscdi=true