Abstract
Electronic excitations in dilute solutions of poly para phenylene ethynylene (poly-PPE) are studied using a QM/MM approach combining many-body Green's functions theory within the GW approximation and the Bethe-Salpeter equation with polarizable force field models. Oligomers up to a length of 7.5 nm (10 repeat units) functionalized with nonyl side chains are solvated in toluene and water, respectively. After equilibration using atomistic molecular dynamics (MD), the system is partitioned into a quantum region (backbone) embedded into a classical (side chains and solvent) environment. Optical absorption properties are calculated solving the coupled QM/MM system self-consistently and special attention is paid to the effects of solvents. The model allows to differentiate the influence of oligomer conformation induced by the solvation from electronic effects related to local electric fields and polarization. It is found that the electronic environment contributions are negligible compared to the conformational dynamics of the conjugated PPE. An analysis of the electron-hole wave function reveals a sensitivity of energy and localization characteristics of the excited states to bends in the global conformation of the oligomer rather than to the relative of phenyl rings along the backbone.
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B.S. Gaylord, A.J. Heeger, G.C. Bazan, Proc. Natl. Acad. Sci. 99, 10954 (2002)
S.A. Kushon, K.D. Ley, K. Bradford, R.M. Jones, D. McBranch, D. Whitten, Langmuir 18, 7245 (2002)
B.S. Harrison, M.B. Ramey, J.R. Reynolds, K.S. Schanze, J. Amer. Chem. Soc. 122, 8561 (2000)
D.T. McQuade, A.E. Pullen, T.M. Swager, Chem. Rev. 100, 2537 (2000)
I.B. Kim, A. Dunkhorst, J. Gilbert, U.H.F. Bunz, Macromol. 38, 4560 (2005)
M. Liu, P. Kaur, D.H. Waldeck, C. Xue, H. Liu, Langmuir 21, 1687 (2005)
F. Hide, M.A. Diaz-Garcia, B.J. Schwartz, M.R. Andersson, Q. Pei, A.J. Heeger, Science 273, 1833 (1996)
P.K.H. Ho, J.S. Kim, J.H. Burroughes, H. Becker, S.F.Y. Li, T.M. Brown, F. Cacialli, R.H. Friend, Nature 404, 481 (2000)
C. Zhang, D. Braun, A.J. Heeger, J. Appl. Phys. 73, 5177 (1993)
P. Kaur, H. Yue, M. Wu, M. Liu, J. Treece, D.H. Waldeck, C. Xue, H. Liu, J. Phys. Chem. B 111, 8589 (2007)
S. Shaheen, D. Ginley, G. Jabbour, MRS Bull. 30, 10 (2005)
C.J. Brabec, S. Gowrisanker, J.J.M. Halls, D. Laird, S. Jia, S.P. Williams, Adv. Mater. 22, 3839 (2010)
C. Wu, B. Bull, C. Szymanski, K. Christensen, J. McNeill, ACS Nano 2, 2415 (2008)
C.E. Halkyard, M.E. Rampey, L. Kloppenburg, S.L. Studer-Martinez, U.H.F. Bunz, Macromol. 31, 8655 (1998)
D. Tuncel, H.V. Demir, Nanoscale 2, 484 (2010)
H. Yue, M. Wu, C. Xue, S. Velayudham, H. Liu, D.H. Waldeck, J. Phys. Chem. B 112, 8218 (2008)
N. Vukmirovi, L.W. Wang, J. Phys. Chem. 128, 121102 (2008)
N. Vukmirovi, L.W. Wang, Nano Lett. 9, 3996 (2009)
D.P. McMahon, A. Troisi, Chem. Phys. Lett. 480, 210 (2009)
Y.H. Chan, C. Wu, F. Ye, Y. Jin, P.B. Smith, D.T. Chiu, Anal. Chem. 83, 1448 (2011)
G. Onida, L. Reining, A. Rubio, Rev. Mod. Phys. 74, 601 (2002)
X. Blase, C. Attaccalite, V. Olevano, Phys. Rev. B 83, 115103 (2011)
B. Baumeier, D. Andrienko, M. Rohlfing, J. Chem. Theory Comput. 8, 2790 (2012)
N. Marom, F. Caruso, X. Ren, O.T. Hofmann, T. Körzdörfer, J.R. Chelikowsky, A. Rubio, M. Schefflẽr, P. Rinke, Phys. Rev. B 86, 245127 (2012)
M.J. van Setten, F. Weigend, F. Evers, J. Chem. Theory Comput. 9, 232 (2013)
X. Blase, C. Attaccalite, Appl. Phys. Lett. 99, 171909 (2011)
B. Baumeier, D. Andrienko, Y. Ma, M. Rohlfing, J. Chem. Theory Comput. 8, 997 (2012)
B. Baumeier, M. Rohlfing, D. Andrienko, J. Chem. Theory Comput. 10, 3104 (2014)
W.L. Jorgensen, J.D. Madura, C.J. Swenson, J. Am. Chem. Soc. 106, 6638 (1984)
W.L. Jorgensen, D.S. Maxwell, J. Tirado-Rives, J. Am. Chem. Soc. 118, 11225 (1996)
E.K. Watkins, W.L. Jorgensen, J. Phys. Chem. A 105, 4118 (2001)
S. Maskey, F. Pierce, D. Perahia, G.S. Grest, J. Chem. Phys. 134, 244906 (2011)
S. Maskey, N.C. Osti, D. Perahia, G.S. Grest, ACS Macro Letters 2, 700 (2013)
B. Bagheri, B. Baumeier, M. Karttunen, arxiv: http://arxiv.org/abs/1605.02554 (2016) (submitted)
H.J.C. Berendsen, J.R. Grigera, T.P. Straatsma, J. Chem. Phys. 91, 6269 (1987)
J. Wong-ekkabut, M. Karttunen, Biochimica et Biophysica Acta (BBA) - Biomembranes, in press, doi: 10.1016/j.bbamem.2016.02.004 (2016)
D. Van Der Spoel, E. Lindahl, B. Hess, G. Groenhof, A.E. Mark, H.J.C. Berendsen, J. Comput. Chem. 26, 1701 (2005)
T. Darden, D. York, L. Pedersen, J. Chem. Phys. 98, 10089 (1993)
U. Essmann, L. Perera, M.L. Berkowitz, T. Darden, H. Lee, L.G. Pedersen, J. Chem. Phys. 103, 8577 (1995)
G.A. Cisneros, M. Karttunen, P. Ren, C. Sagui, Chem. Rev. 114, 779 (2014)
L. Verlet, Phys. Rev. 159, 98 (1967)
G.S. Grest, K. Kremer, Phys. Rev. A 33, 3628 (1986)
M. Parrinello, J. Appl. Phys. 52, 7182 (1981)
W. Humphrey, A. Dalke, K. Schulten, J. Mol. Graphics 14, 33 (1996)
L. Hedin, S. Lundqvist, in Solid State Physics: Advances in Research and Application, Vol. 23 (Academix Press, New York, 1969), p. 1
For typical donor molecules used in organic solar cells, we showed that the use of the TDA overestimates π-π transition energies by 0.2 eV but yields correct character of the excitations [27]
F. Neese, Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2, 73 (2012)
A.D. Becke, J. Chem. Phys. 98, 5648 (1993)
C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37, 785 (1988)
S.H. Vosko, L. Wilk, M. Nusair, Canadian J. Phys. 58, 1200 (1980)
P.J. Stephens, F.J. Devlin, C.F. Chabalowski, M.J. Frisch, J. Phys. Chem. 98, 11623 (1994)
A. Bergner, M. Dolg, W. Küchle, H. Stoll, H. Preuß, Mol. Phys. 80, 1431 (1993)
R. Krishnan, J.S. Binkley, R. Seeger, J.A. Pople, J. Chem. Phys. 72, 650 (1980)
The use of ECPs offers a computational advantage as the wave functions entering the GW procedure are smooth close to the nuclei and do not require strongly localized basis functions, keeping the numerical effort tractable. We confirmed that the Kohn-Sham energies obtained from ECP-based calculations do not deviate significantly from all-electron results
Y. Ma, M. Rohlfing, C. Molteni, Phys. Rev. B 80, 241405 (2009)
Y. Ma, M. Rohlfing, C. Molteni, J. Chem. Theory Comput. 6, 257 (2010)
V. Rühle, A. Lukyanov, F. May, M. Schrader, T. Vehoff, J. Kirkpatrick, B. Baumeier, D. Andrienko, J. Chem. Theory Comput. 7, 3335 (2011)
Available on www.votca.org
C. Risko, M.D. McGehee, J.L. Bredas, Chem. Sci. 2, 1200 (2011)
F. May, B. Baumeier, C. Lennartz, D. Andrienko, Phys. Rev. Lett. 109, 136401 (2012)
B. Lunkenheimer, A. Köhn, J. Chem. Theory Comput. 9, 977 (2013)
T. Schwabe, K. Sneskov, J.M. Haugaard Olsen, J. Kongsted, O. Christiansen, C. Hättig, J. Chem. Theory Comput. 8, 3274 (2012)
A. Stone, The Theory of Intermolecular Forces, 2nd edn. (Oxford University Press, Oxford, 2013), ISBN 978-0-19-967239-4
B. Thole, Chem. Phys. 59, 341 (1981)
P.T. van Duijnen, M. Swart, J. Phys. Chem. A 102, 2399 (1998)
C.M. Breneman, K.B. Wiberg, J. Comput. Chem. 11, 361 (1990)
F. Weigend, R. Ahlrichs, Phys. Chem. Chem. Phys. 7, 3297 (2005)
S. Grimme, J. Comput. Chem. 27, 1787 (2006)
D. Perahia, R. Traiphol, U.H.F. Bunz, Macromol. 34, 151 (2001)
U.H.F. Bunz, Macromol. Rapid Commun. 30, 772 (2009)
T. Miteva, L. Palmer, L. Kloppenburg, D. Neher, U.H.F. Bunz, Macromol. 33(3), 652 (2000)
H. Kong, G. He, Mol. Simul. 41, 1060 (2015)
A. Hariharan, J.G. Harris, J. Chem. Phys. 101, 4156 (1994)
N. Reuter, A. Dejaegere, B. Maigret, M. Karplus, J. Phys. Chem. A 104, 1720 (2000)
In the evaluation of the total QM/MM energy, the contribution resulting from the interactions of the static MM partial charges is neglected, since we are ultimately only interested in total energy differences. Note that we do, however, account for the effect of the electric field of these charges on the polarizable quantum and classical parts
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Bagheri, B., Karttunen, M. & Baumeier, B. Solvent effects on optical excitations of poly para phenylene ethynylene studied by QM/MM simulations based on many-body Green's functions theory. Eur. Phys. J. Spec. Top. 225, 1743–1756 (2016). https://doi.org/10.1140/epjst/e2016-60144-5
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DOI: https://doi.org/10.1140/epjst/e2016-60144-5