[en] A semiempirical quantum-chemical model based on a fragment orbital formalism is presented to assess molecular parameters relevant to charge transport in organic crystals. The mixed valence bond/Hartree-Fock approach provides an efficient integrated framework to evaluate the electronic polarization effects induced by localized charge carriers and the associated impact on the matrix elements mediating electron migration in the hopping regime. This formalism, applied here to anthracene clusters of increasing sizes and dimensionalities, yields the electrostatic and polarization contributions to the total interaction energy of the neutral and charged aggregates and leads to a reduction in the effective bandwidth by ~10%-20% as a result of the polarization cloud.
Disciplines :
Chemistry Physics
Author, co-author :
Castet, F.
Aurel, Ph.
Fritsch, A.
Ducasse, L.
Liotard, D.
Linares, M.
Cornil, Jérôme ; Université de Mons > Faculté des Sciences > Chimie des matériaux nouveaux
Beljonne, David ; Université de Mons > Faculté de Médecine et de Pharmacie > Chimie générale, organique et biomédicale ; Université de Mons > Faculté des Sciences > Chimie des matériaux nouveaux
Language :
English
Title :
Electronic Polarization Effects on Charge Carriers in Anthracene: A Valence Bond Study
Publication date :
24 March 2008
Journal title :
Physical Review. B, Condensed Matter
ISSN :
0163-1829
Publisher :
American Physical Society, Moldova
Volume :
77
Issue :
11
Pages :
115210, 1-14
Peer reviewed :
Peer Reviewed verified by ORBi
Research unit :
S817 - Chimie des matériaux nouveaux
Research institute :
R400 - Institut de Recherche en Science et Ingénierie des Matériaux
See, for example, Chem. Rev. (Washington, D.C.) CHREAY 0009-2665 107 (2007), special issue.
W. Warta and N. Karl, Phys. Rev. B PRBMDO 0163-1829 10.1103/PhysRevB.32. 1172 32, 1172 (1985).
V. Coropceanu, J. Cornil, D. A. da Silva Filho, Y. Olivier, R. Silbey, and J. L. Brédas, Chem. Rev. (Washington, D.C.) CHREAY 0009-2665 10.1021/cr050140x 107, 926 (2007).
A. Troisi and G. Orlandi, Phys. Rev. Lett. PRLTAO 0031-9007 10.1103/PhysRevLett.96.086601 96, 086601 (2006).
M. Hultell and S. Stafström, Chem. Phys. Lett. CHPLBC 0009-2614 10.1016/j.cplett.2006.07.042 428, 446 (2006).
R. A. Marcus, Rev. Mod. Phys. RMPHAT 0034-6861 10.1103/RevModPhys.65.599 65, 599 (1993).
Y. Olivier, V. Lemaur, J. L. Bredas, and J. Cornil, J. Phys. Chem. A JPCAFH 1089-5639 10.1021/jp0571933 110, 6356 (2006).
E. F. Valeev, V. Coropceanu, D. A. da Silva, S. Salman, and J. L. Bredas, J. Am. Chem. Soc. JACSAT 0002-7863 10.1021/ja061827h 128, 9882 (2006);
K. Senthilkumar, F. C. Grozema, F. M. Bickelhaupt, and L. D. A. Siebbeles, J. Chem. Phys. JCPSA6 0021-9606 10.1063/1.1615476 119, 9809 (2003).
F. Castet, A. Fritsch, and L. Ducasse, J. Phys. I JPGCE8 1155-4304 10.1051/jp1:1996231 6, 583 (1996).
F. Castet, L. Ducasse, and A. Fritsch, Chem. Phys. CMPHC2 0301-0104 10.1016/S0301-0104(98)00090-1 232, 37 (1998).
F. Castet, L. Ducasse, and A. Fritsch, J. Chem. Phys. JCPSA6 0021-9606 10.1063/1.481710 112, 10625 (2000).
G. Brunaud, F. Castet, A. Fritsch, M. Kreissler, and L. Ducasse, J. Phys. Chem. B JPCBFK 1089-5647 105, 12665 (2001).
G. Brunaud, F. Castet, A. Fritsch, and L. Ducasse, Phys. Chem. Chem. Phys. PPCPFQ 1463-9076 10.1039/b208655g 4, 6072 (2002).
G. Brunaud, F. Castet, A. Fritsch, and L. Ducasse, Phys. Chem. Chem. Phys. PPCPFQ 1463-9076 10.1039/b300807j 5, 2104 (2003).
F. Castet, A. Fritsch, and L. Ducasse, Int. J. Quantum Chem. IJQCB2 0020-7608 10.1002/qua.20838 106, 734 (2006).
M. J. S. Dewar, R. C. Bingham, and D. H. Lo, J. Am. Chem. Soc. JACSAT 0002-7863 10.1021/ja00839a001 97, 1285 (1975).
M. J. S. Dewar and W. Thiel, J. Am. Chem. Soc. JACSAT 0002-7863 10.1021/ja00457a004 99, 4899 (1977).
M. J. S. Dewar, E. G. Zoebisch, E. F. Healy, and J. J. P. Stewart, J. Am. Chem. Soc. JACSAT 0002-7863 10.1021/ja00299a024 107, 3902 (1985).
J. J. P. Stewart, J. Comput. Chem. JCCHDD 0192-8651 10.1002/jcc.540100208 10, 209 (1989).
J. Li and R. McWeeny, Int. J. Quantum Chem. IJQCB2 0020-7608 10.1002/qua.10293 89, 208 (2002).
P. O. Löwdin, Phys. Rev. PHRVAO 0031-899X 10.1103/PhysRev.97.1474 97, 1474 (1955).
C. P. Brock and J. D. Dunitz, Acta Crystallogr., Sect. B: Struct. Sci. ASBSDK 0108-7681 10.1107/S0108768190008382 46, 795 (1990).
See EPAPS document No. E-PRBMDO-77-090811 for the figures provided in this document, which are labeled S1-S5 in the text. This document can be reached through a direct link in the online article's HTML reference section or via the EPAPS home page (http://www.aip.org/pubser's/epaps.html).
The tensorial components of the quadrupole moment have been obtained indirectly by applying a scaling factor adjusted to reproduce the experimental data for benzene. See I. Eisenstein and R. W. Munn, Chem. Phys. CMPHC2 0301-0104 10.1016/0301-0104(83)85064-2 77, 47 (1983).
C. L. Cheng, D. S. N. Murthy, and G. L. D. Ritchie, Aust. J. Chem. AJCHAS 0004-9425 25, 1301 (1972);
R. J. W. LeFevre, L. Radom, and G. L. D. Ritchie, J. Chem Soc. B JCSPAC 0045-6470 775, 507 (1968).
S. Verlaak and P. Heremans, Phys. Rev. B PRBMDO 0163-1829 10.1103/PhysRevB.75.115127 75, 115127 (2007).
E. A. Silinsh and V. Čápek, Organic Molecular Crystals (AIP, New York, 1994).
E. V. Tsiper and Z. G. Soos, Phys. Rev. B PRBMDO 0163-1829 10.1103/PhysRevB.64.195124 64, 195124 (2001).
E. Clementi, C. C. J. Roothan, and M. Yoshimine, Phys. Rev. PHRVAO 0031-899X 10.1103/PhysRev.127.1618 127, 1618 (1962).
A Troisi and G. Orlandi, J. Phys. Chem. A JPCAFH 1089-5639 10.1021/jp055432g 110, 4065 (2006).
R. M. Glaeser and R. S. Berry, J. Chem. Phys. JCPSA6 0021-9606 10.1063/1.1726537 44, 3797 (1966).
P. Petelenz, Chem. Phys. Lett. CHPLBC 0009-2614 103, 369 (1984).
M. N. Bussac, J. D. Picon, and L. Zuppiroli, Europhys. Lett. EULEEJ 0295-5075 10.1209/epl/i2003-10218-8 66, 392 (2004).
J. L. Brédas, D. Beljonne, V. Coropceanu, and J. Cornil, Chem. Rev. (Washington, D.C.) CHREAY 0009-2665 10.1021/cr040084k 104, 4971 (2004), and references therein.
E. F. Valeev, V. Coropceanu, D. A. da Silva Filho, S. Salman, and J. L. Brédas, J. Am. Chem. Soc. JACSAT 0002-7863 10.1021/ja061827h 128, 9882 (2006).
K. Senthilkumar, F. C. Grozema, C. F. Guerra, F. M. Bickelhaupt, F. D. Lewis, Y. A. Berlin, M. A. Ratner, and L. D. A. Siebbeles, J. Am. Chem. Soc. JACSAT 0002-7863 10.1021/ja054257e 127, 14894 (2005).
K. Senthilkumar, F. C. Grozema, F. M. Bickelhaupt, and L. D. A. Siebbeles, J. Chem. Phys. JCPSA6 0021-9606 10.1063/1.1615476 119, 9809 (2003).
A. A. Voityuk, J. Jortner, M. Bixon, and N. Rösch, J. Chem. Phys. JCPSA6 0021-9606 10.1063/1.1352035 114, 5614 (2001);
N. Leulliot, M. Ghomi, G. Scalmani, and G. Berthier, J. Phys. Chem. JPCHAX 0022-3654 103, 8716 (1999);
I. Daizadeh, J. N. Gehlen, and A. A. Stuchebrukhov, J. Chem. Phys. JCPSA6 0021-9606 10.1063/1.473586 106, 5658 (1997);
D. J. Katz, and A. A. Stuchebrukhov, J. Chem. Phys. JCPSA6 0021-9606 10.1063/1.477107 109, 4960 (1998).
