van der Waals interactions are critical in Car-Parrinello molecular dynamics simulations of porphyrin-fullerene dyads

Topi Karilainen, Oana Cramariuc (Corresponding Author), Mikael Kuisma, Kirsi Tappura, Terttu I. Hukka (Corresponding Author)

    Research output: Contribution to journalArticleScientificpeer-review

    3 Citations (Scopus)

    Abstract

    The interplay between electrostatic and van der Waals (vdW) interactions in porphyrin-C60 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-C60 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 C60 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 C60. 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, C60 can withdraw electrons from porphyrin if it is sufficiently close.
    Original languageEnglish
    Pages (from-to)612-621
    JournalJournal of Computational Chemistry
    Volume36
    Issue number9
    DOIs
    Publication statusPublished - 2015
    MoE publication typeA1 Journal article-refereed

    Fingerprint

    Porphyrin
    Fullerenes
    Van Der Waals
    Porphyrins
    Molecular Dynamics Simulation
    Molecular dynamics
    Railroad cars
    Electrons
    Computer simulation
    Interaction
    Electron
    Amides
    Density functional theory
    Charge transfer
    Electrostatics
    Charge Transfer
    Density Functional
    Affine transformation
    Inclusion
    C60-porphyrin

    Keywords

    • porphyrin
    • fullerene
    • Car-Parrinello molecular dynamics
    • time-dependent-density functional theory

    Cite this

    Karilainen, Topi ; Cramariuc, Oana ; Kuisma, Mikael ; Tappura, Kirsi ; Hukka, Terttu I. / van der Waals interactions are critical in Car-Parrinello molecular dynamics simulations of porphyrin-fullerene dyads. In: Journal of Computational Chemistry. 2015 ; Vol. 36, No. 9. pp. 612-621.
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    title = "van der Waals interactions are critical in Car-Parrinello molecular dynamics simulations of porphyrin-fullerene dyads",
    abstract = "The interplay between electrostatic and van der Waals (vdW) interactions in porphyrin-C60 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-C60 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 C60 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 C60. 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, C60 can withdraw electrons from porphyrin if it is sufficiently close.",
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    author = "Topi Karilainen and Oana Cramariuc and Mikael Kuisma and Kirsi Tappura and Hukka, {Terttu I.}",
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    van der Waals interactions are critical in Car-Parrinello molecular dynamics simulations of porphyrin-fullerene dyads. / Karilainen, Topi; Cramariuc, Oana (Corresponding Author); Kuisma, Mikael; Tappura, Kirsi; Hukka, Terttu I. (Corresponding Author).

    In: Journal of Computational Chemistry, Vol. 36, No. 9, 2015, p. 612-621.

    Research output: Contribution to journalArticleScientificpeer-review

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    AU - Karilainen, Topi

    AU - Cramariuc, Oana

    AU - Kuisma, Mikael

    AU - Tappura, Kirsi

    AU - Hukka, Terttu I.

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    N2 - The interplay between electrostatic and van der Waals (vdW) interactions in porphyrin-C60 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-C60 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 C60 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 C60. 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, C60 can withdraw electrons from porphyrin if it is sufficiently close.

    AB - The interplay between electrostatic and van der Waals (vdW) interactions in porphyrin-C60 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-C60 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 C60 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 C60. 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, C60 can withdraw electrons from porphyrin if it is sufficiently close.

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