{"id":5405,"date":"2011-11-04T09:56:26","date_gmt":"2011-11-04T09:56:26","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=5405"},"modified":"2011-11-07T22:21:00","modified_gmt":"2011-11-07T22:21:00","slug":"chemistry-in-an-attosecond","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=5405","title":{"rendered":"Chemistry in an attosecond."},"content":{"rendered":"<div class=\"kcite-section\" kcite-section-id=\"5405\">\n<p>An attosecond is 10<sup>-18<\/sup>s. The chemistry that takes place on this timescale is called electron dynamics. For example, it is the time taken for an electron to traverse the 1s orbit in a hydrogen atom. And chemists are starting to manipulate electrons (and hence chemistry) on this timescale; for example a recent article (DOI: <a href=\"http:\/\/dx.doi.org\/10.1021\/ja206193t\" target=\"_blank\">10.1021\/ja206193t<\/a>) describes how to control the electrons in benzene using attosecond laser pulses.<\/p>\n<p><a href=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/11\/benzene.svg\"><img decoding=\"async\" class=\"aligncenter size-full wp-image-5406\" title=\"benzene\" src=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/11\/benzene.svg\" alt=\"\" \/><\/a><\/p>\n<p>The diagram above is famously attributed to Kekul\u00e9, and we now teach that this diagram represents resonance structures. This term implies electron (rather than nuclear) dynamics, which results in us only being able to observe an averaged structure with six equivalent C-C bonds. Kekul\u00e9 himself (see <a href=\"http:\/\/dx.doi.org\/10.1021\/cr0300946\" target=\"_blank\">this review<\/a>) could have no way of knowing what the timescale was that his representation implied, but he certainly must have thought it was fast. What is rarely mentioned in textbooks however is how fast it actually is. If the timescale were to be less then say a nanosecond (10<sup>-9<\/sup>s) then we would classify such a process not as a resonance but as a <strong>valence isomerism<\/strong>. This does implicate nuclear motions, and such would be the appropriate description for the isomerism of say cyclo-octatetraene, which is famously slow enough to observe by NMR (see\u00a0<a href=\"http:\/\/dx.doi.org\/10.1039\/P29920001951%20\" target=\"_blank\">10.1039\/P29920001951<\/a>). If the timescale were to be\u00a0a femtosecond (10<sup>-15<\/sup>s) this would correspond to molecular vibrations, and benzene indeed has an observable normal vibrational mode that corresponds more or less to the representation above (the hydrogens also wag a bit). This mode even has a name, the <a href=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=485\" target=\"_blank\">Kekul\u00e9 mode<\/a>. But even this is not fast enough for the intent of the diagram above, which describes what the electrons (and not any moving nuclei) are up to.<\/p>\n<p>The article I mentioned at the start, by Inga Ulusoy and Mathias Nest probes exactly this aspect at the attosecond timescale. More particularly, they look into how to shape an ultra-short laser pulse to excite the electrons into excited states of benzene. This act destroys the aromaticity of the molecule, and changes the electron dynamics in the process. I should quote them here: &#8220;We have shown that by controlling the electron dynamics we can selectively switch benzene\u00a0into nonaromatic target states. These target states exhibit an ultra-fast bidirectional electron circulation\u00a0around the ring system.&#8221;<\/p>\n<p>This is the chemistry in (a few) attosecond(s) that I titled this blog. Whilst the article noted here is theoretical, there seems little doubt that experimental studies of chemistry in an attosecond will became more common, and who knows what surprises await us. Exciting times (sorry about the pun).<\/p>\n<p>I would conclude by mentioning the other extreme, chemistry in an exasecond (10<sup>18<\/sup>s). This happens to correspond more or less to the age of the universe! As it happens, it is not that difficult to come up with chemical processes that occur on this timescale. Any (unimolecular) process that has a free energy barrier larger than that inferred using <em>e.g.<\/em> the equation\u00a0Ln k\/T = 23.76 \u2013 \u0394G\/RT would fit. An example might be the half life for the enantiomerisation of alanine (left to its own devices, and not interfered with by e.g. catalysts).<\/p>\n<!-- kcite active, but no citations found -->\n<\/div> <!-- kcite-section 5405 -->","protected":false},"excerpt":{"rendered":"<p>An attosecond is 10-18s. The chemistry that takes place on this timescale is called electron dynamics. For example, it is the time taken for an electron to traverse the 1s orbit in a hydrogen atom. And chemists are starting to manipulate electrons (and hence chemistry) on this timescale; for example a recent article (DOI: 10.1021\/ja206193t) [&hellip;]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"_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":false,"jetpack_social_options":{"image_generator_settings":{"template":"highway","default_image_id":0,"font":"","enabled":false},"version":2},"jetpack_post_was_ever_published":false},"categories":[1,4],"tags":[752,742,739,206,304,740,743,741,373],"ppma_author":[2661],"class_list":["post-5405","post","type-post","status-publish","format-standard","hentry","category-general","category-interesting-chemistry","tag-attosecond","tag-chemical-processes","tag-exasecond","tag-free-energy-barrier","tag-grt","tag-inga-ulusoy","tag-laser","tag-mathias-nest","tag-tutorial-material"],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v27.7 - https:\/\/yoast.com\/product\/yoast-seo-wordpress\/ -->\n<title>Chemistry in an attosecond. - Henry Rzepa&#039;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=5405\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Chemistry in an attosecond. - Henry Rzepa&#039;s Blog\" \/>\n<meta property=\"og:description\" content=\"An attosecond is 10-18s. The chemistry that takes place on this timescale is called electron dynamics. For example, it is the time taken for an electron to traverse the 1s orbit in a hydrogen atom. And chemists are starting to manipulate electrons (and hence chemistry) on this timescale; for example a recent article (DOI: 10.1021\/ja206193t) [&hellip;]\" \/>\n<meta property=\"og:url\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=5405\" \/>\n<meta property=\"og:site_name\" content=\"Henry Rzepa&#039;s Blog\" \/>\n<meta property=\"article:published_time\" content=\"2011-11-04T09:56:26+00:00\" \/>\n<meta property=\"article:modified_time\" content=\"2011-11-07T22:21:00+00:00\" \/>\n<meta property=\"og:image\" content=\"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/11\/benzene.svg\" \/>\n<meta name=\"author\" content=\"Henry Rzepa\" \/>\n<meta name=\"twitter:card\" content=\"summary_large_image\" \/>\n<meta name=\"twitter:label1\" content=\"Written by\" \/>\n\t<meta name=\"twitter:data1\" content=\"Henry Rzepa\" \/>\n\t<meta name=\"twitter:label2\" content=\"Estimated reading time\" \/>\n\t<meta name=\"twitter:data2\" content=\"3 minutes\" \/>\n<!-- \/ Yoast SEO plugin. -->","yoast_head_json":{"title":"Chemistry in an attosecond. - Henry Rzepa&#039;s Blog","robots":{"index":"index","follow":"follow","max-snippet":"max-snippet:-1","max-image-preview":"max-image-preview:large","max-video-preview":"max-video-preview:-1"},"canonical":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=5405","og_locale":"en_GB","og_type":"article","og_title":"Chemistry in an attosecond. - Henry Rzepa&#039;s Blog","og_description":"An attosecond is 10-18s. The chemistry that takes place on this timescale is called electron dynamics. For example, it is the time taken for an electron to traverse the 1s orbit in a hydrogen atom. And chemists are starting to manipulate electrons (and hence chemistry) on this timescale; for example a recent article (DOI: 10.1021\/ja206193t) [&hellip;]","og_url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=5405","og_site_name":"Henry Rzepa&#039;s Blog","article_published_time":"2011-11-04T09:56:26+00:00","article_modified_time":"2011-11-07T22:21:00+00:00","og_image":[{"url":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/11\/benzene.svg","type":"","width":"","height":""}],"author":"Henry Rzepa","twitter_card":"summary_large_image","twitter_misc":{"Written by":"Henry Rzepa","Estimated reading time":"3 minutes"},"schema":{"@context":"https:\/\/schema.org","@graph":[{"@type":"Article","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=5405#article","isPartOf":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=5405"},"author":{"name":"Henry Rzepa","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#\/schema\/person\/2b40f7b9c872a4dc1547e040a11b6281"},"headline":"Chemistry in an attosecond.","datePublished":"2011-11-04T09:56:26+00:00","dateModified":"2011-11-07T22:21:00+00:00","mainEntityOfPage":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=5405"},"wordCount":530,"commentCount":1,"image":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=5405#primaryimage"},"thumbnailUrl":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/11\/benzene.svg","keywords":["attosecond","chemical processes","exasecond","free energy barrier","G\/RT","Inga Ulusoy","laser","Mathias Nest","Tutorial material"],"articleSection":["General","Interesting chemistry"],"inLanguage":"en-GB","potentialAction":[{"@type":"CommentAction","name":"Comment","target":["https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=5405#respond"]}]},{"@type":"WebPage","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=5405","url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=5405","name":"Chemistry in an attosecond. - 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Generations of chemists have learnt early on in their studies of the subject that these two representations of where the electron pairs in benzene might be located (formally called electronic resonance or valence bond forms) each contribute ~50% to the\u2026","rel":"","context":"In &quot;Interesting chemistry&quot;","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"The Kekule structures of benzene.","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2009\/06\/benzene.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":6543,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=6543","url_meta":{"origin":5405,"position":1},"title":"The Dieneone-phenol controversies.","author":"Henry Rzepa","date":"April 30, 2012","format":false,"excerpt":"During the 1960s, a holy grail of synthetic chemists was to devise an efficient route to steroids. R. B. Woodward was one the chemists who undertook this challenge, starting from compounds known as dienones (e.g. 1) and their mysterious conversion to phenols (e.g. 2 or 3) under acidic conditions. This\u2026","rel":"","context":"In &quot;Chemical IT&quot;","block_context":{"text":"Chemical IT","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=2"},"img":{"alt_text":"","src":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2012\/04\/patha.svg","width":350,"height":200},"classes":[]},{"id":12329,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=12329","url_meta":{"origin":5405,"position":2},"title":"More (blog) connections spotted. Something new about diphenyl magnesium?","author":"Henry Rzepa","date":"April 17, 2014","format":false,"excerpt":"I have just noticed unexpected links between two old posts, one about benzene, one about diphenyl magnesium\u00a0and\u00a0a link to August Kekul\u00e9.\u2020 The post about benzene dealt with the apparently simple issue of why all the C-C bonds are of equal length. The answer, in brief is purely because of the\u2026","rel":"","context":"In &quot;Interesting chemistry&quot;","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":17858,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=17858","url_meta":{"origin":5405,"position":3},"title":"First, hexacoordinate carbon \u2013 now pentacoordinate oxygen?","author":"Henry Rzepa","date":"March 25, 2017","format":false,"excerpt":"The previous post demonstrated the simple iso-electronic progression from six-coordinate carbon to five coordinate nitrogen. Here, a further progression to oxygen is investigated computationally. The systems are formally constructed from a cyclobutadienyl di-anion and firstly the HO5+ cation, giving a tri-cationic complex. There are no examples of the resulting motif\u00a0in\u2026","rel":"","context":"In &quot;Bond slam&quot;","block_context":{"text":"Bond slam","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=2237"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":15552,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=15552","url_meta":{"origin":5405,"position":4},"title":"VSEPR Theory: A closer look at trifluorothionitrile, NSF3.","author":"Henry Rzepa","date":"January 16, 2016","format":false,"excerpt":"The post on applying VSEPR (\"valence shell electron pair repulsion\") theory to the geometry of ClF3\u00a0has proved perennially popular. So here is a follow-up on another little molecue,\u00a0F3SN. As the name implies, it is often represented with an\u00a0S\u2261N bond. Here I take a look at the conventional analysis. This is\u2026","rel":"","context":"In &quot;Hypervalency&quot;","block_context":{"text":"Hypervalency","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=7"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":13962,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13962","url_meta":{"origin":5405,"position":5},"title":"A new way of exploring the directing influence of (electron donating) substituents on benzene.","author":"Henry Rzepa","date":"April 17, 2015","format":false,"excerpt":"The knowledge that substituents on a benzene ring direct an electrophile engaged in a ring substitution reaction according to whether they withdraw or donate electrons is very old. Introductory organic chemistry tells us that electron donating substituents promote the ortho and para positions over the meta. Here I try to\u2026","rel":"","context":"In &quot;Chemical IT&quot;","block_context":{"text":"Chemical IT","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=2"},"img":{"alt_text":"","src":"","width":0,"height":0},"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\/5405","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=5405"}],"version-history":[{"count":0,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/5405\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=5405"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=5405"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=5405"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=5405"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}