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Herein, employing core\u2010level spectroscopy methods combined with density functional theory (DFT) modeling, the modification of the graphenes\u2019 valence band (VB) upon its derivatization by carboxyls and ketones is revealed. The appearance of a set of localized states in the VB of graphene related to molecular orbitals of the introduced functionalities is signified both experimentally and theoretically. Applying the DFT calculations of the density of states projected on the functional groups, their contributions to the VB structure are decomposed. An empirical approach, allowing one to analyze and predict the impact of a certain functional group on the graphenes\u2019 electronic structure in terms of examination of the model molecules, mimicking the introduced functionality, is proposed and validated. The interpretation of the arising states origin is made and their designation, pointing out their symmetry type, is proposed. Taken together, these results guide the band structure engineering of graphene derivatives and give a hint on the mechanisms underlying the alteration of the VB structure of 2D materials upon their derivatization.<\/jats:p>","DOI":"10.1002\/smll.202104316","type":"journal-article","created":{"date-parts":[[2021,10,27]],"date-time":"2021-10-27T10:11:19Z","timestamp":1635329479000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":37,"title":["Valence Band Structure Engineering in Graphene Derivatives"],"prefix":"10.1002","volume":"17","author":[{"given":"Vladimir V.","family":"Shnitov","sequence":"first","affiliation":[{"name":"Ioffe Institute  Politekhnicheskaya St. 26 Saint Petersburg 194021 Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Maxim K.","family":"Rabchinskii","sequence":"additional","affiliation":[{"name":"Ioffe Institute  Politekhnicheskaya St. 26 Saint Petersburg 194021 Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1978-3901","authenticated-orcid":false,"given":"Maria","family":"Brzhezinskaya","sequence":"additional","affiliation":[{"name":"Helmholtz\u2010Zentrum Berlin f\u00fcr Materialien und Energie  Hahn\u2010Meitner\u2010Platz 1 14109 Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dina Yu.","family":"Stolyarova","sequence":"additional","affiliation":[{"name":"NRC \u201cKurchatov Institute\u201d  Akademika Kurchatova pl. 1 Moscow 123182 Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sergey V.","family":"Pavlov","sequence":"additional","affiliation":[{"name":"Center for Computational and Data\u2010Intensive Science and Engineering Skolkovo Institute of Science and Technology  Skolkovo Innovation Center, Nobel St. 3 Moscow 143026 Russia"},{"name":"Joint Institute for High Temperatures of RAS  13\/2 Izhorskaya St. Moscow 125412 Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marina V.","family":"Baidakova","sequence":"additional","affiliation":[{"name":"Ioffe Institute  Politekhnicheskaya St. 26 Saint Petersburg 194021 Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Aleksandr V.","family":"Shvidchenko","sequence":"additional","affiliation":[{"name":"Ioffe Institute  Politekhnicheskaya St. 26 Saint Petersburg 194021 Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Vitaliy A.","family":"Kislenko","sequence":"additional","affiliation":[{"name":"Center for Computational and Data\u2010Intensive Science and Engineering Skolkovo Institute of Science and Technology  Skolkovo Innovation Center, Nobel St. 3 Moscow 143026 Russia"},{"name":"Joint Institute for High Temperatures of RAS  13\/2 Izhorskaya St. Moscow 125412 Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sergey A.","family":"Kislenko","sequence":"additional","affiliation":[{"name":"Joint Institute for High Temperatures of RAS  13\/2 Izhorskaya St. Moscow 125412 Russia"},{"name":"Moscow Institute of Physics and Technology  9 Institutskiy per. 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