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Experimental first absorption energies of Chl\u2005a and b isolated in\u2005vacuo and tagged with quaternary ammonium cations are reported. The energies are largely insensitive to details of the tag structure, a finding supported by first\u2010principles calculations using time\u2010dependent density functional theory. Absorption is significantly blue\u2010shifted compared to that of Chl\u2010containing proteins (by 30\u201370\u2005nm). A single red\u2010shifting perturbation, such as axial ligation or the protein medium, is insufficient to account even for the smallest shift; the largest requires pigment\u2013pigment interactions.<\/jats:p>","DOI":"10.1002\/anie.201410899","type":"journal-article","created":{"date-parts":[[2014,12,30]],"date-time":"2014-12-30T21:01:34Z","timestamp":1419973294000},"page":"2170-2173","source":"Crossref","is-referenced-by-count":63,"title":["Unraveling the Intrinsic Color of Chlorophyll"],"prefix":"10.1002","volume":"54","author":[{"given":"Bruce F.","family":"Milne","sequence":"first","affiliation":[]},{"given":"Yoni","family":"Toker","sequence":"additional","affiliation":[]},{"given":"Angel","family":"Rubio","sequence":"additional","affiliation":[]},{"given":"Steen Br\u00f8ndsted","family":"Nielsen","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2014,12,30]]},"reference":[{"key":"e_1_2_2_1_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-1-4615-2033-7"},{"key":"e_1_2_2_2_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2ee23013e"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1039\/C1FD00078K"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/B513086G"},{"key":"e_1_2_2_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr9904009"},{"key":"e_1_2_2_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470125830.ch1"},{"key":"e_1_2_2_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/ijch.201400006"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1039\/c1sc00313e"},{"key":"e_1_2_2_9_2","first-page":"3649","volume":"9","author":"Marenich A. 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