{"id":28931,"date":"2025-06-25T12:32:26","date_gmt":"2025-06-25T11:32:26","guid":{"rendered":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28931"},"modified":"2025-07-22T09:00:13","modified_gmt":"2025-07-22T08:00:13","slug":"watoc-2025-report-extending-the-limits-of-computation-accuracy","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28931","title":{"rendered":"WATOC 2025 report – extending the limits of computation (accuracy)."},"content":{"rendered":"
\n

This are just a few insights\u00a0I have got from some of the talks I attended.\u00a0As usual, this does not represent a report on the WATOC congress itself, but simply some aspects that caught my personal eye.<\/p>\n

    \n
  1. Frank Neese talked about his Bubblepole approximation for large molecules.[1]<\/a><\/span> And he was not kidding – large. Lets say a DFT calculation at the Def2-TZVPP basis set level (often the level used in this blog). Thus Crambin + 500H2<\/sub>O, which is 2142 atoms can not only be done at this basis set level (33,562 basis functions) but at the astonishing Def2-QZVPP level (rarely attempted here!) with 86,667 basis functions. But that is not the largest – he has also done unhydrated Crambin octamer (5132 atoms) with 116,904 basis functions using the Bubblepole method. Currently this method appears only in his ORCA code – and if I understood correctly they are still working on first and second derivatives. So it will be a little while longer before e.g.<\/i> reaction transition states for such sizes appear, but probably not that long!<\/li>\n
  2. Martin Head Gordon is responsible for the highly regarded \u03c9B97 set of DFT functionals (again used throughout this blog). Until now, the most recent of these, \u03c9B97M(2) from 2019[2]<\/a><\/span> had represented a significant advance in accuracy (let’s say reaction barrier heights) over the previous generations, this having a mean error of ~0.9 kcal\/mol compared to 2-3 kcal\/mol for earlier generations. At the conference he introduced a “Carefully Optimised and Appropriately Constrained Hybrid<\/i>” or COACH functional. He introduced 17 constraints or exact conditions that an ideal functional should have\u00a0and explained that COACH satisfied 12 of these (another relatively recent functional, SCAN satisfies all 17[3]<\/a><\/span>). Earlier functionals satisfy ~6 or less. For 7 selected properties, including barrier heights, the mean errors are around \u00bd to \u2153 of earlier functionals such as the veritable B3LYP+D4 dispersion. His concluding remarks suggested that DFT as such is nearing the ultimate limit of general purpose accuracy achievable by such procedures. I hope to be trying out e.g.<\/i> COACH here in the next year or so.<\/li>\n
  3. Fritz Schaefer “threw the kitchen sink” at the small tetra-atomic fulminic acid, or HCNO, to try to answer the simple question – is it bent or linear?[4]<\/a><\/span> At the CBS (complete basis set) limit and the CCSDTQ(P) level of coupled cluster theory (wow!), the answer converges to the conclusion that it is linear! This level cannot be that far off an exact solution of the Schroedinger equation – and it agrees with experiment!<\/li>\n
  4. Oh,\u00a0a general observation,\u00a0machine learning permeates the entire congress.<\/li>\n<\/ol>\n

    References<\/h2>\n
    1. F. Neese, P. Colinet, B. DeSouza, B. Helmich-Paris, F. Wennmohs, and U. Becker, \"The \u201cBubblepole\u201d (BUPO) Method for Linear-Scaling Coulomb Matrix Construction with or without Density Fitting\", The Journal of Physical Chemistry A<\/i>, vol. 129, pp. 2618-2637, 2025. https:\/\/doi.org\/10.1021\/acs.jpca.4c07415<\/a>\n\n<\/li>\n
    2. N. Mardirossian, and M. Head-Gordon, \"Survival of the most transferable at the top of Jacob\u2019s ladder: Defining and testing the <i>\u03c9<\/i>B97M(2) double hybrid density functional\", The Journal of Chemical Physics<\/i>, vol. 148, 2018. https:\/\/doi.org\/10.1063\/1.5025226<\/a>\n\n<\/li>\n
    3. J.W. Furness, A.D. Kaplan, J. Ning, J.P. Perdew, and J. Sun, \"Accurate and Numerically Efficient r<sup>2<\/sup>SCAN Meta-Generalized Gradient Approximation\", The Journal of Physical Chemistry Letters<\/i>, vol. 11, pp. 8208-8215, 2020. https:\/\/doi.org\/10.1021\/acs.jpclett.0c02405<\/a>\n\n<\/li>\n
    4. A.M. Allen, L.N. Olive Dornshuld, P.A. Gonzalez Franco, W.D. Allen, and H.F. Schaefer, \"Tests of the DFT Ladder for the Fulminic Acid Challenge\", Journal of the American Chemical Society<\/i>, vol. 147, pp. 14088-14104, 2025. https:\/\/doi.org\/10.1021\/jacs.4c13823<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

      This are just a few insights\u00a0I have got from some of the talks I attended.\u00a0As usual, this does not represent a report on the WATOC congress itself, but simply some aspects that caught my personal eye. Frank Neese talked about his Bubblepole approximation for large molecules. And he was not kidding – large. Lets say […]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"jetpack_post_was_ever_published":false,"_jetpack_newsletter_access":"","_jetpack_dont_email_post_to_subs":false,"_jetpack_newsletter_tier_id":0,"_jetpack_memberships_contains_paywalled_content":false,"_jetpack_memberships_contains_paid_content":false,"activitypub_content_warning":"","activitypub_content_visibility":"","activitypub_max_image_attachments":5,"activitypub_interaction_policy_quote":"anyone","activitypub_status":"","footnotes":"","jetpack_publicize_message":"","jetpack_publicize_feature_enabled":true,"jetpack_social_post_already_shared":true,"jetpack_social_options":{"image_generator_settings":{"template":"highway","default_image_id":0,"font":"","enabled":false},"version":2}},"categories":[2238],"tags":[],"ppma_author":[2661],"class_list":["post-28931","post","type-post","status-publish","format-standard","hentry","category-watoc-reports"],"yoast_head":"\nWATOC 2025 report - extending the limits of computation (accuracy). - Henry Rzepa's Blog<\/title>\n<meta name=\"robots\" content=\"index, follow, max-snippet:-1, max-image-preview:large, max-video-preview:-1\" \/>\n<link rel=\"canonical\" href=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28931\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"WATOC 2025 report - extending the limits of computation (accuracy). - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"This are just a few insights\u00a0I have got from some of the talks I attended.\u00a0As usual, this does not represent a report on the WATOC congress itself, but simply some aspects that caught my personal eye. 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In contrast, the heavier perfluoro-octane has an m.p. of -25\u00b0C. Why the difference? Firstly, the crystal structure is shown below, albeit as a dimer rather than a periodic lattice (click on image\u2026","rel":"","context":"With 2 comments","block_context":{"text":"With 2 comments","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25521#comments"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":25918,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25918","url_meta":{"origin":28931,"position":1},"title":"A ROR Persistent Identifier for the WATOC organisation – helping to make scientific connections.","author":"Henry Rzepa","date":"March 9, 2023","format":false,"excerpt":"Science frequently works by people making connections between related (or even apparently unrelated) concepts or data. There are many ways of helping people make these connections - attending a conference or seminar, searching journals for published articles and nowadays also searching for data are just a few examples. For about\u2026","rel":"","context":"In "WATOC reports"","block_context":{"text":"WATOC reports","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=2238"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":25304,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=25304","url_meta":{"origin":28931,"position":2},"title":"Personal Impressions from WATOC 2020 – Dispersion and non Born-Oppenheimer models.","author":"Henry Rzepa","date":"July 11, 2022","format":false,"excerpt":"WATOC 2020 was just held in 2022 in Vancouver Canada, over one week. With many lectures held in parallel, it is not possible for one person to cover anything like the topics presented, so this is a personal view of some of those talks that I attended. As happens with\u2026","rel":"","context":"In "WATOC reports"","block_context":{"text":"WATOC reports","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=2238"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":18730,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=18730","url_meta":{"origin":28931,"position":3},"title":"WATOC 2017 report.","author":"Henry Rzepa","date":"August 29, 2017","format":false,"excerpt":"The triennial conference is this year located in Munich. With 1500 participants and six parallel sessions, this report can give only a flavour of proceedings. Edward Valeev talked about the scaling problem in coupled cluster theories, the so-called gold standard for computing the energy and properties of small molecules. The\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2017\/08\/watoc2017.jpg?resize=350%2C200","width":350,"height":200,"srcset":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2017\/08\/watoc2017.jpg?resize=350%2C200 1x, https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2017\/08\/watoc2017.jpg?resize=525%2C300 1.5x"},"classes":[]},{"id":26199,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=26199","url_meta":{"origin":28931,"position":4},"title":"Blue blood.","author":"Henry Rzepa","date":"August 7, 2023","format":false,"excerpt":"Respiratory pigments are metalloproteins that transport O2, the best known being the bright red\/crimson coloured hemoglobin in human blood. The colour derives from Fe2+ at the core of a tetraporphyrin ring. But less well known is blue blood, and here the colour derives from an oxyhemocyanin unit based on Cu1+\u2026","rel":"","context":"In "crystal_structure_mining"","block_context":{"text":"crystal_structure_mining","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=1745"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2023\/08\/Screenshot57.jpg?resize=350%2C200&ssl=1","width":350,"height":200,"srcset":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2023\/08\/Screenshot57.jpg?resize=350%2C200&ssl=1 1x, https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2023\/08\/Screenshot57.jpg?resize=525%2C300&ssl=1 1.5x, https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2023\/08\/Screenshot57.jpg?resize=700%2C400&ssl=1 2x, https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2023\/08\/Screenshot57.jpg?resize=1050%2C600&ssl=1 3x, https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2023\/08\/Screenshot57.jpg?resize=1400%2C800&ssl=1 4x"},"classes":[]},{"id":28920,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=28920","url_meta":{"origin":28931,"position":5},"title":"WATOC25 and its (Dr Who like) regeneration to Young WATOC25.","author":"Henry Rzepa","date":"June 21, 2025","format":false,"excerpt":"The WATOC congresses occur every three years. WATOC25, the 13th in a series which started in 1987 \u00a0takes places tomorrow in Oslo, Norway, The day before the main event there is something new - a session just for early career researchers or \"Young WATOC\". As an \"old\" WATOCer, I dropped\u2026","rel":"","context":"In "WATOC reports"","block_context":{"text":"WATOC reports","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=2238"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2025\/06\/IMG_2858.jpeg?resize=350%2C200&ssl=1","width":350,"height":200,"srcset":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2025\/06\/IMG_2858.jpeg?resize=350%2C200&ssl=1 1x, https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2025\/06\/IMG_2858.jpeg?resize=525%2C300&ssl=1 1.5x, https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2025\/06\/IMG_2858.jpeg?resize=700%2C400&ssl=1 2x, https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2025\/06\/IMG_2858.jpeg?resize=1050%2C600&ssl=1 3x"},"classes":[]}],"jetpack_likes_enabled":false,"authors":[{"term_id":2661,"user_id":1,"is_guest":0,"slug":"admin","display_name":"Henry Rzepa","avatar_url":"https:\/\/secure.gravatar.com\/avatar\/897b6740f7f599bca7942cdf7d7914af5988937ae0e3869ab09aebb87f26a731?s=96&d=blank&r=g","0":null,"1":"","2":"","3":"","4":"","5":"","6":"","7":"","8":""}],"_links":{"self":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/28931","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=28931"}],"version-history":[{"count":17,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/28931\/revisions"}],"predecessor-version":[{"id":28948,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/28931\/revisions\/28948"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=28931"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=28931"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=28931"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=28931"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}