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<article article-type="research-article" dtd-version="1.1" xml:lang="en"><front xmlns:ali="http://www.niso.org/schemas/ali/1.0/" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns:c="http://ns.iop.org/namespaces/content" xmlns:fn="http://www.w3.org/2005/xpath-functions" xmlns:m="http://ns.iop.org/namespaces/meta"><journal-meta><journal-id journal-id-type="publisher-id">est</journal-id><journal-title-group><journal-title xml:lang="en">Electronic Structure</journal-title><abbrev-journal-title abbrev-type="IOP" xml:lang="en">EST</abbrev-journal-title><abbrev-journal-title abbrev-type="publisher" xml:lang="en">Electron. Struct.</abbrev-journal-title></journal-title-group><issn pub-type="epub">2516-1075</issn><publisher><publisher-name>IOP Publishing</publisher-name></publisher></journal-meta><article-meta><article-id pub-id-type="publisher-id">estabd487</article-id><article-id pub-id-type="doi">10.1088/2516-1075/abd487</article-id><article-id pub-id-type="manuscript">abd487</article-id><article-id pub-id-type="other">EST-100142.R1</article-id><article-categories><subj-group subj-group-type="display-article-type"><subject>Paper</subject></subj-group></article-categories><title-group><article-title>Zero-point energies prevent a trigonal to simple cubic transition in high-pressure sulfur</article-title></title-group><contrib-group><contrib contrib-type="author" corresp="yes" xlink:type="simple"><contrib-id authenticated="false" contrib-id-type="orcid">0000-0001-9350-7115</contrib-id><name name-style="western"><surname>Whaley-Baldwin</surname><given-names>Jack</given-names></name><xref ref-type="aff" rid="affiliation01">1</xref><xref ref-type="fn" rid="estabd487afn1">*</xref><email>jajw4@cam.ac.uk</email></contrib><aff id="affiliation01">
               <label>1</label>TCM Group, Cavendish Laboratory, <institution xlink:type="simple">University of Cambridge, United Kingdom</institution>
            </aff></contrib-group><author-notes><fn id="estabd487afn1"><label>2</label><p>Author to whom any correspondence should be addressed.</p></fn></author-notes><pub-date pub-type="ppub"><month>12</month><year>2020</year></pub-date><pub-date pub-type="epub"><day>7</day><month>1</month><year>2021</year></pub-date><pub-date pub-type="open-access"><day>7</day><month>1</month><year>2021</year></pub-date><volume>2</volume><issue>4</issue><elocation-id content-type="artnum">045003</elocation-id><supplementary-material content-type="suppdata" id="ESTabd487supp1" orientation="portrait" position="float" xlink:href="https://cfn-live-content-bucket-iop-org.s3.amazonaws.com/journals/2516-1075/2/4/045003/5/ESTabd487supp1.pdf?AWSAccessKeyId=AKIAYDKQL6LTV7YY2HIK&amp;Expires=1612281429&amp;Signature=DqO9VdiICeeL%2BelrS7%2FDS7c84NE%3D" xlink:type="simple"><label>Supplementary data</label></supplementary-material><history><date date-type="received"><day>9</day><month>10</month><year>2020</year></date><date date-type="rev-recd"><day>12</day><month>12</month><year>2020</year></date><date date-type="accepted"><day>17</day><month>12</month><year>2020</year></date><date date-type="oa-requested"><day>15</day><month>12</month><year>2020</year></date></history><permissions><copyright-statement>© 2021 The Author(s). Published by IOP Publishing Ltd</copyright-statement><copyright-year>2021</copyright-year><license license-type="cc-by" xlink:href="https://creativecommons.org/licenses/by/4.0/" xlink:type="simple"><license-p>
                  <graphic content-type="print" orientation="portrait" position="float" xlink:href="https://cfn-live-content-bucket-iop-org.s3.amazonaws.com/journals/2516-1075/2/4/045003/5/estabd487license.eps?AWSAccessKeyId=AKIAYDKQL6LTV7YY2HIK&amp;Expires=1612281429&amp;Signature=jRnvmL3H%2FwCQHNJL6WHSGVtTYYw%3D" xlink:type="simple"/>
                  <graphic content-type="online" orientation="portrait" position="float" xlink:href="https://cfn-live-content-bucket-iop-org.s3.amazonaws.com/journals/2516-1075/2/4/045003/5/estabd487license.gif?AWSAccessKeyId=AKIAYDKQL6LTV7YY2HIK&amp;Expires=1612281429&amp;Signature=dbc62RzZM%2Fzp1IaD1iLQcemJrpg%3D" xlink:type="simple"/>Original content from this work may be used under the terms of the <ext-link ext-link-type="uri" xlink:href="https://creativecommons.org/licenses/by/4.0/" xlink:type="simple">Creative Commons Attribution 4.0 licence</ext-link>. Any further distribution of this work must maintain attribution to the author(s) and the title of the work, journal citation and DOI.</license-p></license></permissions><self-uri content-type="pdf" xlink:href="https://cfn-live-content-bucket-iop-org.s3.amazonaws.com/journals/2516-1075/2/4/045003/5/est_2_4_045003.pdf?AWSAccessKeyId=AKIAYDKQL6LTV7YY2HIK&amp;Expires=1612281429&amp;Signature=jIIDrcq6vQ1szNuldPy9yNsBD%2F0%3D" xlink:type="simple"/><abstract><title>Abstract</title><p>Recently published density functional theory results using the PBE functional (Whaley-Baldwin and Needs 2020 <italic toggle="yes">New J. Phys.</italic> 22 023020) suggest that elemental sulfur does not adopt the simple-cubic (SC) <inline-formula>
                  <tex-math><?CDATA $Pm\bar{3}m$?></tex-math>
                  <mml:math display="inline" overflow="scroll"><mml:mi>P</mml:mi><mml:mi>m</mml:mi><mml:mrow><mml:mover accent="true"><mml:mrow><mml:mn>3</mml:mn></mml:mrow><mml:mo>̄</mml:mo></mml:mover></mml:mrow><mml:mi>m</mml:mi></mml:math>
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               </inline-formula> phase at high pressures, in disagreement with previous works (Rudin and Liu 1999 <italic toggle="yes">Phys. Rev. Lett.</italic> 
               <bold>83</bold> 3049--52; Gavryushkin <italic toggle="yes">et al</italic> 2017 <italic toggle="yes">Phys. Status Solidi</italic> B <bold>254</bold> 1600857). We carry out an extensive set of calculations using a variety of different exchange–correlation functionals (both local and non-local), and show that even though under LDA and PW91 a high-pressure SC phase does indeed become favourable at the static lattice level, when zero-point energies (ZPEs) are included, the transition to the SC phase is suppressed in every case, owing to the larger ZPE of the SC phase; thus confirming the transition sequence as <inline-formula>
                  <tex-math><?CDATA $R\bar{3}m\to $?></tex-math>
                  <mml:math display="inline" overflow="scroll"><mml:mi>R</mml:mi><mml:mrow><mml:mover accent="true"><mml:mrow><mml:mn>3</mml:mn></mml:mrow><mml:mo>̄</mml:mo></mml:mover></mml:mrow><mml:mi>m</mml:mi><mml:mo>→</mml:mo></mml:math>
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               </inline-formula> BCC, with no intervening SC phase. We reproduce these findings with pseudopotentials that explicitly include core electronic states, and show that even at these high pressures, only the <italic toggle="yes">n</italic> = 3 valence shell contributes to bonding in sulfur. We then compare our findings against the all-electron code <monospace>ELK</monospace>, which is in excellent agreement with our pseudopotential results, and examine the roles of the exchange and correlation contributions to the total energy. We further calculate anharmonic vibrational corrections to the ZPEs of the two phases, and find that such corrections are several orders of magnitude smaller than the ZPEs and are thus negligible. The effect of finite temperatures is also considered, and we show that the <inline-formula>
                  <tex-math><?CDATA $Pm\bar{3}m$?></tex-math>
                  <mml:math display="inline" overflow="scroll"><mml:mi>P</mml:mi><mml:mi>m</mml:mi><mml:mrow><mml:mover accent="true"><mml:mrow><mml:mn>3</mml:mn></mml:mrow><mml:mo>̄</mml:mo></mml:mover></mml:mrow><mml:mi>m</mml:mi></mml:math>
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               </inline-formula> phase becomes even more unfavourable with an increase in temperature. Finally, the experimental consequences of our results on the equation of state of sulfur and its superconducting critical temperature are explicitly calculated.</p></abstract><kwd-group kwd-group-type="author"><kwd>high pressure</kwd><kwd>structure searching</kwd><kwd>phase transition</kwd><kwd>solid sulfur</kwd><kwd>phonons</kwd><kwd>anharmonic vibrations</kwd></kwd-group><funding-group><award-group xlink:type="simple"><funding-source xlink:type="simple">Engineering and Physical Sciences Research Council<named-content content-type="funder-id" xlink:type="simple">https://doi.org/10.13039/501100000266</named-content>
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