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van der W aals interactions are critical in C ar– P arrinello molecular dynamics simulations of porphyrin–fullerene dyads
Author(s) -
Karilainen Topi,
Cramariuc Oana,
Kuisma Mikael,
Tappura Kirsi,
Hukka Terttu I.
Publication year - 2015
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.23834
Subject(s) - porphyrin , van der waals force , molecular dynamics , chemistry , chemical physics , density functional theory , population , fullerene , computational chemistry , linker , molecule , photochemistry , organic chemistry , demography , sociology , computer science , operating system
The interplay between electrostatic and van der Waals (vdW) interactions in porphyrin‐C 60 dyads is still under debate despite its importance in influencing the structural characteristics of such complexes considered for various applications in molecular photovoltaics. In this article, we sample the conformational space of a porphyrin‐C 60 dyad using Car–Parrinello molecular dynamics simulations with and without empirical vdW corrections. Long‐range vdW interactions, which are poorly described by the commonly used density functional theory functionals, prove to be essential for a proper dynamics of the dyad moieties. Inclusion of vdW corrections brings porphyrin and C 60 close together in an orientation that is in agreement with experimental observations. The structural differences arising from the vdW corrections are shown to be significant for several properties and potentially less important for others. Additionally, our Mulliken population analysis reveals that contrary to the common belief, porphyrin is not the primary electron donating moiety for C 60 . In the considered dyad, fullerene's affinity for electrons is primarily satisfied by charge transfer from the amide group of the linker. However, we show that in the absence of another suitable bound donor, C 60 can withdraw electrons from porphyrin if it is sufficiently close. © 2015 Wiley Periodicals, Inc.