Au(111)表面一维分子组装中氢键诱导的分子轨道能量位移
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摘要
利用扫描隧道显微术、扫描隧道谱和密度泛函理论研究了茚并[1,2-b]芴-6,12-二酮(IFDO)在Au(111)表面形成的组装结构及其中分子轨道能级的变化.结果表明, IFDO在Au(111)表面通过分子间氢键沿鱼骨重构结构形成一维自组装分子链;位于组装结构中的分子的最低未占轨道相对孤立分子向费米能级方向发生0.16~0.32 e V的位移,且位移大小与分子同周围分子形成氢键的数目和方式有关.通过定量地对比不同氢键环境中分子的轨道能量位移与周围分子极化能大小的变化趋势,发现周围分子的瞬时极性是造成组装结构中IFDO分子轨道能量变化的主要因素.而周围分子的诱导极性则对缺陷结构处分子的轨道能级有不可忽略的影响.实验测得的IFDO分子轨道的能量变化来自于周围分子各向异性的瞬时极性和诱导极性的共同作用.
The self-assembly of indeno[1,2-b]fluorene-6,12-dione(IFDO) absorbed on Au(111) was investigated by scanning tunneling microscopy, scanning tunneling spectroscopy, and density functional theory calculations. It was found that IFDO molecules assembled into one-dimensional molecular chains along the herringbone structures on the Au(111) surface. The lowest unoccupied molecular orbital of IFDO molecules in the assembled structures, relative to isolated molecules, shifts towards Fermi level. The degree of molecular orbital shift, varying from 0.16 to 0.32 eV,depends on the pattern and number of hydrogen bonds formed between the detected IFDO molecule and its neighboring ones. Both transient and induced polarization of neighboring IFDO molecules contribute to the total polarization energy which leads to molecular orbital shift observed by experiments. The former makes the dominant contribution, while the effect of the latter is appreciable especially for molecules composing the defect structures.
The self-assembly of indeno[1,2-b]fluorene-6,12-dione(IFDO) absorbed on Au(111) was investigated by scanning tunneling microscopy, scanning tunneling spectroscopy, and density functional theory calculations. It was found that IFDO molecules assembled into one-dimensional molecular chains along the herringbone structures on the Au(111) surface. The lowest unoccupied molecular orbital of IFDO molecules in the assembled structures, relative to isolated molecules, shifts towards Fermi level. The degree of molecular orbital shift, varying from 0.16 to 0.32 eV,depends on the pattern and number of hydrogen bonds formed between the detected IFDO molecule and its neighboring ones. Both transient and induced polarization of neighboring IFDO molecules contribute to the total polarization energy which leads to molecular orbital shift observed by experiments. The former makes the dominant contribution, while the effect of the latter is appreciable especially for molecules composing the defect structures.
引文
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2 Kahn A,Koch N,Gao W.J Polym Sci B,2003,41:2529-2548
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7 Hesper R,Tjeng LH,Sawatzky GA.Europhys Lett,1997,40:177-182
8 Kr?ger J,Jensen H,Berndt R,Rurali R,Lorente N.Chem Phys Lett,2007,438:249-253
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11 Gonzalez-Lakunza N,Canas-Ventura ME,Ruffieux P,Rieger R,Mullen K,Fasel R,Arnau A?.ChemPhysChem,2009,10:2943-2946
12 Soubatch S,Weiss C,Temirov R,Tautz FS.Phys Rev Lett,2009,102:177405
13 Cochrane KA,Schiffrin A,Roussy TS,Capsoni M,Burke SA.Nat Commun,2015,6:8312
14 Willenbockel M,Stadtmüller B,Sch?nauer K,Bocquet FC,Lüftner D,Reinisch EM,Ules T,Koller G,Kumpf C,Soubatch S,Puschnig P,Ramsey MG,Tautz FS.New J Phys,2013,15:033017
15 Silinsh EA.Organic Molecular Crystals:Their Electronic States.Berlin:Springer,1980
16 Horcas I,Fernández R,Gómez-Rodríguez JM,Colchero J,Gómez-Herrero J,Baro AM.Rev Sci Instrum,2007,78:013705
17 Hohenberg P,Kohn W.Phys Rev,1964,136:B864-B871
18 Kohn W,Sham LJ.Phys Rev,1965,140:A1133-A1138
19 Kresse G,Furthmüller J.Phys Rev B,1996,54:11169-11186
20 Kresse G,Joubert D.Phys Rev B,1999,59:1758-1775
21 Perdew JP,Burke K,Ernzerhof M.Phys Rev Lett,1996,77:3865-3868
22 Perdew JP,Burke K,Ernzerhof M.Phys Rev Lett,1997,78:1396
23 Monkhorst HJ,Pack JD.Phys Rev B,1976,13:5188-5192
24 Frisch MJ,Trucks GW,Schlegel HB,Scuseria GE,Robb MA,Cheeseman JR,Scalmani G,Barone V,Mennucci B,Petersson GA,Nakatsuji H,Caricato M,Li X,Hratchian HP,Izmaylov AF,Bloino J,Zheng G,Sonnenberg JL,Hada M,Ehara M,Toyota K,Fukuda R,Hasegawa J,Ishida M,Nakajima T,Honda Y,Kitao O,Nakai H,Vreven T,J.A.Montgomery J,Peralta JE,Ogliaro F,Bearpark M,Heyd JJ,Brothers E,Kudin KN,Staroverov VN,Kobayashi R,Normand J,Raghavachari K,Rendell A,Burant JC,Iyengar SS,Tomasi J,Cossi M,Rega N,Millam JM,Klene M,Knox JE,Cross JB,Bakken V,Adamo C,Jaramillo J,Gomperts R,Stratmann RE,Yazyev O,Austin AJ,Cammi R,Pomelli C,Ochterski JW,Martin RL,Morokuma K,Zakrzewski VG,Voth GA,Salvador P,Dannenberg JJ,Dapprich S,Daniels AD,Farkas O,Foresman JB,Ortiz JV,Cioslowski J,Fox DJ.Gaussian 09,Revision A.02.Wallingford CT:Gaussian Inc.,2009
25 Becke AD.J Chem Phys,1993,98:5648-5652
26 Stephens PJ,Devlin FJ,Chabalowski CF,Frisch MJ.J Phys Chem,1994,98:11623-11627
27 Reed AE,Curtiss LA,Weinhold F.Chem Rev,1988,88:899-926
28 Glendening ED,Reed AE,Carpenter JE,Weinhold F.NBO,3.1.Madison:University of Wisconsin,Theoretical Chemistry Institute,1996
29 Chen W,Madhavan V,Jamneala T,Crommie MF.Phys Rev Lett,1998,80:1469-1472
30 Dougherty DB,Maksymovych P,Lee J,Yates Jr.JT.Phys Rev Lett,2006,97:236806
31 Kowalzik P,Atodiresei N,Gingras M,Caciuc V,Schnaebele N,Raimundo JM,Blügel S,Waser R,Karth?user S.Phys Chem Chem Phys,2012,14:1635-1641
32 Zhang YQ,Bj?rk J,Barth JV,Klappenberger F.Nano Lett,2016,16:4274-4281
33 Krygowski TM,Szaty?owicz H,Zachara JE.J Org Chem,2005,70:8859-8865
34 Lenain P,Mandado M,Mosquera RA,Bultinck P.J Phys Chem A,2008,112:7898-7904