Abstract
We investigate the effect of structural fluctuations on charge transfer integrals, overlap integrals, and site energies in a system of two stacked molecular 2,3,6,7,10,11-hexakishexyloxytriphenylene (HAT6), which is a model system for conducting devices in organic photocell applications. A density functional based computational study is reported. Accurate potential energy surface calculations are carried out using an improved meta-hybrid density functional to determine the most stable configuration of the two weakly bound HAT6 molecules. The equilibrium parameters in terms of the twist angle and co-facial separation are calculated. Adopting the fragment approach within the Kohn–Sham density functional framework, these parameters are combined to a lateral slide, to mimic structural/conformational fluctuations and variations in the columnar phase. The charge transfer and spatial overlap integrals, and site energies, which form the matrix element of the Kohn–Sham Hamiltonian are derived. It is found that these quantities are strongly affected by the conformational variations. The spatial overlap between stacked molecules is found to be of considerable importance since charge transfer integrals obtained using the fragment approach differ significantly from those using the dimer approach.
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Schmidt-Mende L, Fechtenkotter A, Multen K, Moons E, Frien RH, MacKenzie JD (2001) Science 293:1119
Forrest SR (2005) Nature (Lond) 87:233508
Xue J, Uchida S, Rand BP, Forrest SR (2004) App Phys Lett 85:5757
Yu, G, Gao J, Hummelen JC, Wudl F, Heeger AJ (1995) Science 270:1789
Peumans P, Uchida S, Forrest SR (2003) Nature 425:158
Xue J, Uchida S, Rand BP, Forrest SR (2004) App Phys Lett 84:3013
Chandrasekhar S, Raganath GS (1990) Rep Prog Phys 53:57
Boden N, Bissel R, Clements J, Movaghar B (1996) Curr Sci 71:599
Shen X, Dong RY, Boden N, Bushby RJ, Martin PS, Wood A (1998) J Chem Phys 108:4324
Adam D, Schumacher B, Simmeree J, Etzbach KH, Ringsdorf H, Haarer D (1994) Nature (Lond) 371:142
Xue J, Uchida S, Rand B, Forrest S (2004) Appl Phys Lett 85:5757
Yang F, Lunt R, Forrest S (2008) Appl Phys Lett 92:053310
Dreschel J, Mannig B, Kozlowski F, Pfeiffer M, Leo K, Hope H (2005) App Phys Lett 86:244102
Cheyns D, Gommans H, Odijk M, Poortmans J, Heremans P (2007) Sol Ener Mat 91:399
Rand BP, Xue J, Yang F, Forrest SR (2005) App Phys Lett 87:233508
Soci C, Moses D, Xu QH, Heeger AJ (2005) Phys Rev B 72:245204
Mulder FM, Stride J, Picken SJ, Kouwer PHJ, de Haas MP, Siebbeles LDA, Kearley GJ (2003) J Am Chem Soc 125:3860
Kruglova O, Mulder FM, Siebbeles LDA, Kearley GJ (2006) Chem Phys 330:333
Kruglova O, Mulder FM, Kotlewski A, Picken SJ, Parker S, Johnson MR, Kearley GJ (2006) Chem Phys 330:360
Kearley GJ, Mulder FM, Picken SJ, Kouwer PHJ, Stride J (2003) Chem Phys 292:185
Hohenberg P, Kohn W (1964) Phys Rev 136:B864–B871
Kohn W, Sham L (1965) Phys Rev 140:A1133
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA Jr, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2004) Gaussian 03, revision d.01. Gaussian, Inc., Wallingford
Perdew JP, Burke K, Ernzerhof M (1996) Phys Rev Lett 77:3865
Rey J, Savin A (1998) Int J Quantum Chem 69:581
Krieger JB, Chen J, Iafrate GJ, Savin A (1996) In: Gonis A, Kioussis N (eds) Electron correlations and materials properties. Plenum, New York, p 463
Toulouse J, Savin A, Adamo C (2002) J Chem Phys 117:10465
Zhao Y, Truhlar DG (2005) J Chem Theory Comput 1:415
Rassolov VA, Ratner MA, Pople JA, Redfern PC, Curtiss LA (2001) J Comput Chem 22:976
Petersson GA, Al-Laham MA (1991) J Chem Phys 94:6081
Raghavachari K, Trucks GW (1989) J Chem Phys 91:1062
ADF, Amsterdam density functional program (2006) Theoretical chemistry. Vrije Universiteit, Amsterdam. http://www.scm.com
te Velde G, Bickelhaupt FM, Baerends EJ, Guerra CF, van Gisbergen SJA, Snijders JG, Ziegler T (2001) J Comput Chem 22:931
Becke A (1988) Phys Rev A 38:3098
Perdew J (1986) Phys Rev B 33:8822
Perdew J (1986) Phys Rev B 34:7406
Perdew J, Chevarya J, Vosko S, Jackson K, Pederson M, Singh D, Fiolhais C (1992) Phys Rev B 46:6671
Lenthe EV, Baerends EJ (2003) J Comput Chem 24:1142
Huang J, Kertesz M (2005) J Chem Phys 122:234707
Senthilkumar K, Grozema FC, Bickelhaupt FM, Siebbeles LDA (2003) J Chem Phys 119:9809
Santhanamoorthi N, Kolandaivel P, Senthilkumar K (2006) J Phys Chem A 110:11551
Wang H-J, Fu Y (2009) J Mol Struct (Theochem) 893:67
Riley KE, Op’t Holt BT, Merz KM (2007) J Chem Theory Comput 3:407
Bartlett RJ, Lotrich VF, Schweigert IV (2005) J Chem Phys 123:062205
Zbiri M, Johnson MR, Kearley GJ, Mulder FM (2009) (in press)
Wegewijs BR, Siebbeles LDA, Boden N, Bushby RJ, Movaghar B, Lozman OR, Liu Q, Pecchia A, Mason LA (2002) Phys Rev B 65:245112
Palenberg MA, Silbey RJ, Malagoli M, Bredas JL (2000) J Chem Phys 112:1541
Vosko SH, Wilk L, Nusair M (1980) Can J Chem 58:1200
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Dedicated to Professor Sandor Suhai on the occasion of his 65th birthday and published as part of the Suhai Festschrift Issue.
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Zbiri, M., Johnson, M.R., Kearley, G.J. et al. Density functional calculations of potential energy surface and charge transfer integrals in molecular triphenylene derivative HAT6 . Theor Chem Acc 125, 445–451 (2010). https://doi.org/10.1007/s00214-009-0559-3
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DOI: https://doi.org/10.1007/s00214-009-0559-3