First-Principles Study of Vibrational Raman Spectra of Amorphous Carbon
NIU Li1,2, ZHU Jia-qi1*, GAO Wei3, DU Shan-yi1
1. Center for Composite Materials and Structure, Harbin Institute of Technology, Harbin 150080, China 2. School of Physics and Electronic Engineering, Harbin Normal University, Harbin 150025, China 3. Key Laboratory for High Energy Density Beam Processing Technology, Beijing Aeronautical Manufacturing Technology Research Institute, Beijing 100024, China
Abstract：The vibrational density of states and nonresonant reduced Raman spectra of amorphous carbon at densities of 2.6, 2.9 and 3.2 g·cm-3 were calculated by the use of a first-principles plane-wave pesudopotential method. Three structural models were generated by liquid-quench method using Car-Parinello molecular dynamics, their vibrational frequencies and eigenmodes were determined using the linear response approach, and Raman coupling tensors were calculated using the finite electric field method. The calculated results show that the sp3 fraction increases from 50% to 84.4%, the sp2 configuration changes from mainly rings to short chains, the position of the G peak moves to higher frequencies, the intensity ratio of D and G peaks decreases, the position of the T peak moves to lower frequencies and the intensity ratio of T and G peaks increases as density increases from 2.6 to 3.2 g·cm-3. The authors’ calculated Raman spectra show an overall good agreement with experimental spectra. The analysis in terms of atomic vibrations confirms that the G and D peaks both come from sp2 C contribution, G peak is due to the stretching vibration of any pair of sp2 atoms and the T peak is due to the C—C sp3 vibration. The authors’ analysis also confirms that the dispersion of G and T peaks is due to bond-length changes. The bond length of chains (olefins) is shorter than that of rings, so their vibrational frequency is higher and the G-peak position moves to higher frequencies with increasing the sp3 fraction. The number of sp3-sp2 type bonds decreases as the sp3 fraction increases. These bonds are shorter than pure sp3-sp3 bonds, hence the T-peak position moves to lower frequencies. The research results provide a theoretic basis for analyzing experimental Raman spectra of amorphous carbon.
Key words：First principles;Amorphous carbon (a-C);Raman spectra;Vibrational density of states (VDOS)
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