Lattice dynamics and disorder-induced contraction in functionalized graphene

The lattice dynamics and disorder-induced contraction in hydrogenated, fluorinated, and chlorinated graphene are studied by first-principles simulation. The effects of the functionalization on the phonon dispersions, Gruneissen constants, vibrational thermodynamic functions (free energy, internal energy, entropy, and heat capacity), thermal-expansion coefficients, and bulk moduli are systematically investigated. Functionalization changes the chemical-bond length, mass, thickness, vibrational-mode symmetry, and mode number, and subsequently has significant effects on the phonon dispersions and Gruneissen constants. Functionalization generally increases the vibrational thermodynamic functions, and their temperature dependences all present conventional isotope effects. Functionalization suppresses (enhances) the thermal contraction (expansion) of the lattice, due to the increases in the system mass, membrane thickness, and the compressibility of the phonons. Both the lattice-constant variation and the phonon thermalization contribute to the temperature dependence of the bulk modulus. Both pristine and hydrogenated graphene can be viewed as two kinds of materials having the Invar and Elinvar properties. The contribution to the lattice contraction in functionalized graphene from the conformation disorder (about 2.0%) is much larger than that by thermalization (<0.1% at 300 K), which explains the mismatch between the experimental and theoretical lattice constants. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4793790]