{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,7,30]],"date-time":"2025-07-30T09:55:59Z","timestamp":1753869359002,"version":"3.41.2"},"reference-count":121,"publisher":"Wiley","issue":"14","license":[{"start":{"date-parts":[[2025,5,24]],"date-time":"2025-05-24T00:00:00Z","timestamp":1748044800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["J Comput Chem"],"published-print":{"date-parts":[[2025,5,30]]},"abstract":"<jats:title>ABSTRACT<\/jats:title><jats:p>Asymmetrically substituted indenotetracene crystals are promising nonfullerene electron transport materials for organic photovoltaics, offering potential improvements in efficiency and stability. In this work, we present a first\u2010principle investigation of the electronic and vibrational properties of a diarylindenotetracene system functionalized with two methoxy groups (hereafter <jats:italic>DimethoxyASI<\/jats:italic>). Single\u2010crystal X\u2010ray diffraction analysis [reported in <jats:italic>J. Org. Chem. 2018, 83, 4, 1828<\/jats:italic>] reveals a monoclinic  structure with an interplanar distance of 3.76 \u00c5, providing insight into the molecular packing and intermolecular interactions that govern the solid\u2010state organization. Notably, for the first time, in this work we identify two distinct dimeric species within the crystalline lattice by a structural and electronic analysis, each exhibiting different intermolecular arrangements that significantly influence both the electronic structure and vibrational properties of the material. Density functional theory (DFT) and time\u2010dependent density functional theory (TDDFT) calculations provide insight into the molecular packing, electronic states, and vibrational characteristics of the crystal. The theoretical absorption spectrum, obtained from TDDFT calculations, features three main electronic transitions centered at 530, 360, and 275 nm, displaying a mixed character of localized excitations and charge\u2010transfer contributions. The vibrational properties, investigated through phonon density of states calculations at the DFT level, highlight well\u2010defined spectral features. While most vibrational modes remain consistent between monomeric and dimeric configurations, significant deviations emerge in the low\u2010frequency region, where intermolecular interactions and crystal packing effects play a crucial role. Furthermore, the two dimeric species exhibit distinct electronic properties beyond their geometric differences. A key distinguishing factor is the transition electric dipole moments (TEDMs), which governs the probability and polarization of electronic transitions. Our analysis reveals that the TEDMs magnitude and orientation vary significantly between the two dimeric species, suggesting that they may interact differently with polarized light. These differences provide new insight into the role of molecular aggregation in shaping the optical response of organic semiconductors and highlight the impact of polymorphism on their electronic properties. Overall, this study underscores the intricate relationship between molecular packing, electronic structure, and vibrational properties in indenotetracene\u2010based materials, contributing to a deeper understanding of their potential applications in optoelectronic devices.<\/jats:p>","DOI":"10.1002\/jcc.70141","type":"journal-article","created":{"date-parts":[[2025,5,24]],"date-time":"2025-05-24T08:00:09Z","timestamp":1748073609000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Electronic Structure and Vibrational Properties of Indenotetracene\u2010Based Crystal"],"prefix":"10.1002","volume":"46","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-5845-4211","authenticated-orcid":false,"given":"Federico","family":"Coppola","sequence":"first","affiliation":[{"name":"Scuola Superiore Meridionale  Napoli Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0009-0000-7426-8745","authenticated-orcid":false,"given":"Raoul","family":"Carfora","sequence":"additional","affiliation":[{"name":"Scuola Superiore Meridionale  Napoli Italy"},{"name":"Department of Chemical Sciences University of Napoli Federico II  Napoli Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2983-766X","authenticated-orcid":false,"given":"Nadia","family":"Rega","sequence":"additional","affiliation":[{"name":"Scuola Superiore Meridionale  Napoli Italy"},{"name":"Department of Chemical Sciences University of Napoli Federico II  Napoli Italy"},{"name":"Istituto Nazionale Di Fisica Nucleare, sezione di Napoli  Napoli Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2025,5,24]]},"reference":[{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/cm049614j"},{"volume-title":"Physical and Chemical Aspects of Organic Electronics: From Fundamentals to Functioning Devices","year":"2009","author":"W\u00f6ll C.","key":"e_1_2_9_3_1"},{"volume-title":"Organic Electronic Materials: Conjugated Polymers and Low Molecular Weight Organic Solids","year":"2013","author":"Farchioni R.","key":"e_1_2_9_4_1"},{"key":"e_1_2_9_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527689545"},{"key":"e_1_2_9_6_1","article-title":"Insight Into Organic Photovoltaic Cell: Prospect and Challenges, Unconv","volume":"5","author":"Nkinyam C. M.","year":"2024","journal-title":"Resources"},{"key":"e_1_2_9_7_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41586-018-0536-x"},{"key":"e_1_2_9_8_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.adj3654"},{"key":"e_1_2_9_9_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41578-022-00514-0"},{"key":"e_1_2_9_10_1","doi-asserted-by":"publisher","DOI":"10.1002\/cptc.202200214"},{"key":"e_1_2_9_11_1","doi-asserted-by":"publisher","DOI":"10.1002\/adfm.202413864"},{"key":"e_1_2_9_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.4c02033"},{"key":"e_1_2_9_13_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.201800388"},{"key":"e_1_2_9_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/cssc.202101067"},{"key":"e_1_2_9_15_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3RA01454A"},{"key":"e_1_2_9_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jctc.2c00063"},{"key":"e_1_2_9_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jctc.0c00919"},{"key":"e_1_2_9_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.9b00494"},{"key":"e_1_2_9_19_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.orgel.2014.03.044"},{"key":"e_1_2_9_20_1","doi-asserted-by":"publisher","DOI":"10.1039\/B512983D"},{"key":"e_1_2_9_21_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2jm15126j"},{"key":"e_1_2_9_22_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.matlet.2012.08.145"},{"key":"e_1_2_9_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemmater.7b00067"},{"key":"e_1_2_9_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/jz301047d"},{"key":"e_1_2_9_25_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.dyepig.2013.01.020"},{"key":"e_1_2_9_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja5092613"},{"key":"e_1_2_9_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b11149"},{"key":"e_1_2_9_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201612090"},{"key":"e_1_2_9_29_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.2711525"},{"key":"e_1_2_9_30_1","doi-asserted-by":"publisher","DOI":"10.1002\/pip.791"},{"key":"e_1_2_9_31_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.3148664"},{"key":"e_1_2_9_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja105260d"},{"key":"e_1_2_9_33_1","doi-asserted-by":"publisher","DOI":"10.1039\/c0ee00668h"},{"key":"e_1_2_9_34_1","doi-asserted-by":"publisher","DOI":"10.1002\/aenm.201000024"},{"key":"e_1_2_9_35_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4MH00042K"},{"key":"e_1_2_9_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.5b00199"},{"key":"e_1_2_9_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b06414"},{"key":"e_1_2_9_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b02808"},{"key":"e_1_2_9_39_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CC07973J"},{"key":"e_1_2_9_40_1","doi-asserted-by":"publisher","DOI":"10.1038\/nmat5063"},{"key":"e_1_2_9_41_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.mtener.2024.101591"},{"key":"e_1_2_9_42_1","doi-asserted-by":"publisher","DOI":"10.1002\/adfm.201805924"},{"key":"e_1_2_9_43_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.200904054"},{"key":"e_1_2_9_44_1","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202214653"},{"key":"e_1_2_9_45_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41570-019-0152-9"},{"key":"e_1_2_9_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.1c00581"},{"key":"e_1_2_9_47_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.3c08366"},{"key":"e_1_2_9_48_1","doi-asserted-by":"publisher","DOI":"10.3390\/molecules28083411"},{"key":"e_1_2_9_49_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.2c05001"},{"key":"e_1_2_9_50_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1SC01238J"},{"key":"e_1_2_9_51_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c03249"},{"key":"e_1_2_9_52_1","doi-asserted-by":"publisher","DOI":"10.1146\/annurev-physchem-040215-112025"},{"key":"e_1_2_9_53_1","doi-asserted-by":"publisher","DOI":"10.1146\/annurev.physchem.56.092503.141314"},{"key":"e_1_2_9_54_1","doi-asserted-by":"publisher","DOI":"10.1021\/ol300098p"},{"key":"e_1_2_9_55_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.7b02756"},{"key":"e_1_2_9_56_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.27231"},{"key":"e_1_2_9_57_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4CP04000G"},{"key":"e_1_2_9_58_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.0c00223"},{"key":"e_1_2_9_59_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jctc.2c00794"},{"key":"e_1_2_9_60_1","doi-asserted-by":"publisher","DOI":"10.1063\/5.0085512"},{"key":"e_1_2_9_61_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.4c00934"},{"key":"e_1_2_9_62_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr1002613"},{"key":"e_1_2_9_63_1","doi-asserted-by":"publisher","DOI":"10.1146\/annurev-physchem-040412-110130"},{"key":"e_1_2_9_64_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.7b00601"},{"key":"e_1_2_9_65_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar300193r"},{"key":"e_1_2_9_66_1","first-page":"5929","article-title":"Femtosecond Raman Microscopy Reveals Structural Dynamics Leading to Triplet Separation in Rubrene Singlet Fission","volume":"8","author":"Bera K.","year":"2017","journal-title":"Journal of Physical Chemistry"},{"key":"e_1_2_9_67_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.0c06725"},{"key":"e_1_2_9_68_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpclett.3c02845"},{"key":"e_1_2_9_69_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3TA00193H"},{"key":"e_1_2_9_70_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c05518"},{"key":"e_1_2_9_71_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja104123r"},{"key":"e_1_2_9_72_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.201302427"},{"key":"e_1_2_9_73_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1232994"},{"key":"e_1_2_9_74_1","doi-asserted-by":"publisher","DOI":"10.1002\/9781119578826.ch16"},{"key":"e_1_2_9_75_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1736034"},{"key":"e_1_2_9_76_1","doi-asserted-by":"publisher","DOI":"10.1366\/14-07707"},{"key":"e_1_2_9_77_1","doi-asserted-by":"publisher","DOI":"10.1080\/00387010.2018.1501704"},{"key":"e_1_2_9_78_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1TC01698A"},{"key":"e_1_2_9_79_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527814596.ch15"},{"key":"e_1_2_9_80_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.82.035208"},{"key":"e_1_2_9_81_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.3625293"},{"key":"e_1_2_9_82_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRev.136.B864"},{"key":"e_1_2_9_83_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRev.140.A1133"},{"key":"e_1_2_9_84_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.76.12.6062"},{"key":"e_1_2_9_85_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.52.997"},{"key":"e_1_2_9_86_1","doi-asserted-by":"publisher","DOI":"10.1142\/2914"},{"key":"e_1_2_9_87_1","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(96)00440-X"},{"key":"e_1_2_9_88_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.475855"},{"key":"e_1_2_9_89_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.477483"},{"key":"e_1_2_9_90_1","doi-asserted-by":"publisher","DOI":"10.1146\/annurev.physchem.55.091602.094449"},{"key":"e_1_2_9_91_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.2173258"},{"key":"e_1_2_9_92_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr0505627"},{"key":"e_1_2_9_93_1","doi-asserted-by":"publisher","DOI":"10.1146\/annurev-physchem-032511-143803"},{"key":"e_1_2_9_94_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.464913"},{"key":"e_1_2_9_95_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.540040303"},{"key":"e_1_2_9_96_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.447079"},{"key":"e_1_2_9_97_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cplett.2004.06.011"},{"key":"e_1_2_9_98_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cplett.2005.12.040"},{"key":"e_1_2_9_99_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp063376t"},{"key":"e_1_2_9_100_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.2831900"},{"key":"e_1_2_9_101_1","doi-asserted-by":"publisher","DOI":"10.1039\/c002428g"},{"key":"e_1_2_9_102_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp911329g"},{"key":"e_1_2_9_103_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1558471"},{"key":"e_1_2_9_104_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.471637"},{"key":"e_1_2_9_105_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-94-011-3262-6_2"},{"key":"e_1_2_9_106_1","doi-asserted-by":"publisher","DOI":"10.1021\/ct200651r"},{"key":"e_1_2_9_107_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0009-2614(99)01149-5"},{"key":"e_1_2_9_108_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1313558"},{"key":"e_1_2_9_109_1","doi-asserted-by":"crossref","unstructured":"I.TammandI.Tamm \u201cRelativistic Interaction of Elementary Particles Selected Papers \u201d 157\u2013174(1991).","DOI":"10.1007\/978-3-642-74626-0_12"},{"key":"e_1_2_9_110_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRev.78.382"},{"key":"e_1_2_9_111_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jctc.7b00699"},{"volume-title":"Gaussian16 Revision C.01","year":"2016","author":"Frisch M. J.","key":"e_1_2_9_112_1"},{"key":"e_1_2_9_113_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.092143399"},{"key":"e_1_2_9_114_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr050140x"},{"key":"e_1_2_9_115_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2CS00481J"},{"key":"e_1_2_9_116_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200604045"},{"key":"e_1_2_9_117_1","doi-asserted-by":"publisher","DOI":"10.1002\/admi.202200815"},{"key":"e_1_2_9_118_1","doi-asserted-by":"publisher","DOI":"10.1039\/b804317e"},{"key":"e_1_2_9_119_1","doi-asserted-by":"publisher","DOI":"10.3390\/cryst6040041"},{"key":"e_1_2_9_120_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.70.104106"},{"key":"e_1_2_9_121_1","doi-asserted-by":"publisher","DOI":"10.1063\/5.0065496"},{"key":"e_1_2_9_122_1","doi-asserted-by":"publisher","DOI":"10.1039\/b810993a"}],"container-title":["Journal of Computational Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/jcc.70141","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,5,31]],"date-time":"2025-05-31T10:37:31Z","timestamp":1748687851000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/jcc.70141"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,5,24]]},"references-count":121,"journal-issue":{"issue":"14","published-print":{"date-parts":[[2025,5,30]]}},"alternative-id":["10.1002\/jcc.70141"],"URL":"https:\/\/doi.org\/10.1002\/jcc.70141","archive":["Portico"],"relation":{},"ISSN":["0192-8651","1096-987X"],"issn-type":[{"type":"print","value":"0192-8651"},{"type":"electronic","value":"1096-987X"}],"subject":[],"published":{"date-parts":[[2025,5,24]]},"assertion":[{"value":"2025-05-06","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-05-09","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-05-24","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e70141"}}