Han, Sang Soo and Yu, Ted H. and Merinov, Boris V. and van Duin, Adri C. T. and Yazami, Rachid and Goddard, William A., III (2010) Unraveling Structural Models of Graphite Fluorides by Density Functional Theory Calculations. Chemistry of Materials, 22 (6). pp. 2142-2154. ISSN 0897-4756 http://resolver.caltech.edu/CaltechAUTHORS:20100415-110231862
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Using density functional theory (DFT) calculations, we have studied structural models of graphite fluorides for five fluorine compositions; C_(1)F (CF_1), C_(2)F (CF_(0.5)), C_(3)F (CF_(0.33)), C_(4)F (CF_(0.25)), and C_(16)F (CF_(0.0625)). For each composition, we considered several possible structural models and calculated heat of formation relative to the pristine graphite and F_2 molecule. We also simulated X-ray diffraction patterns for each structural model and compared those with experiments. We find, in agreement with earlier experiments, that the most stable structure of the C_(1)F (CF_1) has an infinite array of trans-linked cyclohexane chairs of covalent C−F bonds (1.38 Å). We also find that the effects of the layer stacking sequence such as AB or AA′ is not significant. For the C_(2)F (CF_(0.5)) system, an earlier model in the literature indicated that all carbon atoms have only sp^3 hybridization due to coexistence of C−C and C−F covalent bonds. However, in this work, we propose a new C_(2)F (CF_(0.5)) crystal structure in which half of the carbon atoms has sp^3 hybridization due to C−F covalent bonds and the other half has sp^2 hybridization as found in pristine graphite. Besides, with the structural models of graphite fluorides considered in this work, their formation mechanism is also clarified. Initially, two fluorines are positioned at adjacent carbon atoms with the trans geometry, and then, one graphene layer is fully covered with fluorine while other layers are still pristine. After full coverage of the graphene layer, newly added fluorine will get located on this pristine graphene layer, and then, finally, all carbon layers are covered with fluorine leading to formation of C_(1)F crystal. Through this mechanism, we can explain phase transition from the C_(2)F to the C_(1)F through further fluorination, which was demonstrated by an earlier experiment.
|Additional Information:||© 2010 American Chemical Society. Published In Issue: March 23, 2010; article ASAP: February 12, 2010; received: December 14, 2009; revised: January 26, 2010. The facilities of the Materials and Process Simulation Center were supported by ONR-DURIP and ARO-DURIP. S.S.H. was partially supported by the Hydrogen Energy R&D Center, one of the 21st Century Frontier R&Dprogram, funded by theMinistry of Education, Science and Technology of Korea. This work was supported by MARCO/FENA(HJ andWAG).W.A.G. also acknowledges support from the WCU programs through NRF of Korea funded by the MEST (R31-2008-000-10055-0).|
|Official Citation:||Unraveling Structural Models of Graphite Fluorides by Density Functional Theory Calculations Sang Soo Han, Ted H. Yu, Boris V. Merinov, Adri C. T. van Duin, Rachid Yazami, William A. Goddard III Chemistry of Materials 2010 22 (6), 2142-2154|
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|Deposited By:||Jason Perez|
|Deposited On:||16 Apr 2010 18:18|
|Last Modified:||26 Dec 2012 11:58|
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