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Linear-scaling density functional simulations of the effect of crystallographic structure on electronic and optical properties of fullerene solvates

Linear-scaling density functional simulations of the effect of crystallographic structure on electronic and optical properties of fullerene solvates
Linear-scaling density functional simulations of the effect of crystallographic structure on electronic and optical properties of fullerene solvates
In this work crystal properties, HOMO and LUMO energies, band gaps, density of states, as well as the optical absorption spectra of fullerene C60 and its derivative phenyl-C61-butyric-acid-methyl-ester (PCBM) co-crystallised with various solvents such as benzene, biphenyl, cyclohexane, and chlorobenzene were investigated computationally using linear-scaling density functional theory with plane waves as implemented in the ONETEP program. Such solvates are useful materials as electron acceptors for organic photovoltaic (OPV) devices. We found that the fullerene parts contained in the solvates are unstable without solvents, and the interactions between fullerene and solvent molecules in C60 and PCBM solvates have a significant contribution to the cohesive energies of solvates, indicating that solvent molecules are essential to keep C60 and PCBM solvates stable. Both the band gap (Eg) and the HOMO, LUMO states of C60 and PCBM solvates are mainly determined by the fullerene parts contained in solvates. Chlorobenzene- and orthodichlorobenzene-solvated PCBM are the most promising electron-accepting materials among these solvates to increase the driving force for charge separation in OPVs due to their relatively high LUMO energies. The UV-Vis absorption spectra for solvent-free C60 and PCBM crystals in the present work are similar to those for C60 and PCBM thin films shown in literature. Changes in the absorption spectra of C60 solvates relative to the solvent-free C60 crystal are more significant than those of PCBM solvates due to the weaker effect of solvents on the ?-stacking interactions between fullerene molecules in the latter solvates. The main absorptions for all C60 and PCBM crystals locate in the ultraviolet (UV) region
1463-9076
1-20
Xue, Hong-Tao
784078a4-1b02-44eb-863b-ea5831e02585
Boschetto, Gabriele
4b29b31b-e76f-42fe-8b1f-b0556149fb32
Krompiec, Michal
c5280165-053d-422d-8872-ae612852d773
Morse, Graham
5fb82ce2-979f-4357-a250-10f69a95272c
Tang, Fu-Ling
3f18e501-0e6b-4d8d-a4cd-0d55ca99dd2d
Skylaris, Chris
8f593d13-3ace-4558-ba08-04e48211af61
Xue, Hong-Tao
784078a4-1b02-44eb-863b-ea5831e02585
Boschetto, Gabriele
4b29b31b-e76f-42fe-8b1f-b0556149fb32
Krompiec, Michal
c5280165-053d-422d-8872-ae612852d773
Morse, Graham
5fb82ce2-979f-4357-a250-10f69a95272c
Tang, Fu-Ling
3f18e501-0e6b-4d8d-a4cd-0d55ca99dd2d
Skylaris, Chris
8f593d13-3ace-4558-ba08-04e48211af61

Xue, Hong-Tao, Boschetto, Gabriele, Krompiec, Michal, Morse, Graham, Tang, Fu-Ling and Skylaris, Chris (2017) Linear-scaling density functional simulations of the effect of crystallographic structure on electronic and optical properties of fullerene solvates. Physical Chemistry Chemical Physics, 1-20. (doi:10.1039/C6CP08165G).

Record type: Article

Abstract

In this work crystal properties, HOMO and LUMO energies, band gaps, density of states, as well as the optical absorption spectra of fullerene C60 and its derivative phenyl-C61-butyric-acid-methyl-ester (PCBM) co-crystallised with various solvents such as benzene, biphenyl, cyclohexane, and chlorobenzene were investigated computationally using linear-scaling density functional theory with plane waves as implemented in the ONETEP program. Such solvates are useful materials as electron acceptors for organic photovoltaic (OPV) devices. We found that the fullerene parts contained in the solvates are unstable without solvents, and the interactions between fullerene and solvent molecules in C60 and PCBM solvates have a significant contribution to the cohesive energies of solvates, indicating that solvent molecules are essential to keep C60 and PCBM solvates stable. Both the band gap (Eg) and the HOMO, LUMO states of C60 and PCBM solvates are mainly determined by the fullerene parts contained in solvates. Chlorobenzene- and orthodichlorobenzene-solvated PCBM are the most promising electron-accepting materials among these solvates to increase the driving force for charge separation in OPVs due to their relatively high LUMO energies. The UV-Vis absorption spectra for solvent-free C60 and PCBM crystals in the present work are similar to those for C60 and PCBM thin films shown in literature. Changes in the absorption spectra of C60 solvates relative to the solvent-free C60 crystal are more significant than those of PCBM solvates due to the weaker effect of solvents on the ?-stacking interactions between fullerene molecules in the latter solvates. The main absorptions for all C60 and PCBM crystals locate in the ultraviolet (UV) region

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Accepted/In Press date: 11 January 2017
e-pub ahead of print date: 19 January 2017
Published date: 21 February 2017
Additional Information: Funded by National Natural Science Foundation of China (11164014, 11364025)
Organisations: Chemistry

Identifiers

Local EPrints ID: 405020
URI: http://eprints.soton.ac.uk/id/eprint/405020
ISSN: 1463-9076
PURE UUID: 6bff6e81-124d-45f7-8448-631b85dadc4f
ORCID for Gabriele Boschetto: ORCID iD orcid.org/0000-0001-8830-3572
ORCID for Chris Skylaris: ORCID iD orcid.org/0000-0003-0258-3433

Catalogue record

Date deposited: 23 Jan 2017 14:17
Last modified: 07 Oct 2020 04:22

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Contributors

Author: Hong-Tao Xue
Author: Gabriele Boschetto ORCID iD
Author: Michal Krompiec
Author: Graham Morse
Author: Fu-Ling Tang
Author: Chris Skylaris ORCID iD

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