Size variation of infrared vibrational spectra from molecules to hydrogenated diamond nanocrystals: a density functional theory study

Infrared spectra of hydrogenated diamond nanocrystals of one nanometer length are calculated by ab initio methods. Positions of atoms are optimized via density functional theory at the level of the generalized gradient approximation of Perdew, Burke and Ernzerhof (PBE) using 3-21G basis states. The frequencies in the vibrational spectrum are analyzed against reduced masses, force constants and intensities of vibration. The spectrum can be divided into two regions depending on the properties of the vibrations or the gap separating them. In the first region, results show good matching to several experimentally obtained lines. The 500 cm(−1) broad-peak acoustical branch region is characterized by pure C–C vibrations. The optical branch is centered at 1185 cm(−1). Calculations show that several C–C vibrations are mixed with some C–H vibrations in the first region. In the second region the matching also extends to C–H vibration frequencies that include different modes such as symmetric, asymmetric, wagging, scissor, rocking and twisting modes. In order to complete the picture of the size dependence of the vibrational spectra, we analyzed the spectra of ethane and adamantane. The present analysis shows that acoustical and optical branches in diamond nanocrystals approach each other and collapse at 963 cm(−1) in ethane. Variation of the highest reduced-mass-mode C–C vibrations from 1332 cm(−1) of bulk diamond to 963 cm(−1) for ethane (red shift) is shown. The analysis also shows the variation of the radial breathing mode from 0 cm(−1) of bulk diamond to 963 cm(−1) for ethane (blue shift). These variations compare well with experiment. Experimentally, the above-mentioned modes appear shifted from their exact positions due to overlap with neighboring modes.