Role of intermolecular charge delocalization and its dimensionality in efficient band-like electron transport in crystalline 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane (F 2 -TCNQ)

• Published in: Physical chemistry chemical physics : PCCP Vol. 19; no. 37; pp. 25478 - 25486
• Main Author: Sosorev, Andrey Yu
• Format: Journal Article
• Language: English
• Published: England 27.09.2017
• ISSN: 1463-9076; 1463-9084; 1463-9084
• DOI: 10.1039/C7CP04357K

Theoretical understanding of charge transport in organic semiconductors is exclusively important for organic electronics, but still remains a subject of debate. The recently discovered record-high band-like electron mobility in single crystals of 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane (F 2 -TCNQ) is challenging from the theoretical viewpoint. First, the very small size of the F 2 -TCNQ molecule implies high reorganization energy that seems incompatible with efficient charge transport. Second, it is not clear why the crystals of a similar compound, 7,7,8,8-tetracyanoquinodimethane (TCNQ), show an inefficient hopping electron transport mechanism. To address these issues, we apply DFT and QM/MM calculations to the F n -TCNQ ( n = 0,2,4) crystal series. We show that multidimensional intermolecular charge delocalization is of key importance for efficient charge transport in materials consisting of small-sized molecules, and commonly used guidelines for the search for high-mobility organic semiconductors are to be corrected.