New arising bands at 1,419 and 1,516 cm-1 in GO and at 1,500 and 1,555 cm-1 in GNPs could be assigned to the vibrations from the edge atoms, and also according to [14], the first principal calculation showed new emerging bands at 1,450 and 1,530 cm-1. Figure 5 Raman at λ ex  = 785 nm (a) and CARS (b) spectra of GNPs (1) and GO (2). The position of D-mode in CARS and Raman spectra is approximately the same. Besides, it is worthwhile to mark the widening of the D-mode in the case of the CARS spectra of GNPs and the redistribution

between I D and I G in the CARS spectra relatively to the Raman analogues. Another feature of the interrelation between Raman and CARS spectra is observed in the 2,400 to 3,200 cm-1 range. The corresponding spectra of the GNPs are presented in Figure 6. It is seen that the Raman spectrum of the GNPs has a usual form, as represented by the strong 2D-mode at 2,595 cm-1. this website At the same time, this mode is absent in the CARS spectrum, while there

appeared another two strong band frequencies which are 2,460 and 2,960 cm-1 (Figure 6). It could be supposed that the first is a combination of D-mode buy MM-102 with a mode at approximately 1,150 cm-1 (D1) which corresponds to a phonon belonging to a point other than K and Γ of the Brillouin zone [29], and the second is probably a double resonance of the 1,516 cm-1 band. The disappearance of the 2D-mode is supposed to be connected with specificity of the CARS technique and the absence of the conditions for double electron-phonon

resonance. Simultaneously, in the region of the second tones, we registered more bands than the usual, so multiphonon processes [30, 31] could occur more efficiently. Figure 6 CARS (1) and Raman at λ ex  = 785 nm (2) spectra of GNPs. The Thiamet G modes near 2,460 cm-1 as well as those in the region of 2,400 to 3,200 cm-1 are assigned to overtones [26]. Nemanich and Solin [24] have registered a band at 3,250 cm-1 and a weaker band at 2,450 cm-1 in the Raman spectra of graphite. The last band was named as D″ by Vidano and Fishbach [25, 32]. Later, Nemanich and Solin, using polarization measurement, assigned the peaks in the 2,300- to 3,250-cm-1 region to overtones in graphite [24], and the 2,950-cm-1 band to D + D′ (D′-mode at 1,620 cm-1 is due to disorder) rather than to D + G. Vidano and Fishbach [25] confirmed that the 3,250-cm-1 band is the D′ overtone, analogous to the band at 2,700 cm-1 which is the D overtone named G′. Interestingly, those bands do not shift with excitation energy, and the energy dependence of the 2,950-cm-1 band is consistent with D + D′ or D + G. The CARS images of the GNPs obtained using the different bands are presented in Figure 7. The distribution of the intensity of the CARS bands could be obviously seen: the intensities of the bands at 2,460 and 2,960 cm-1 are similar, where the intensity of the signal at 2,960 cm-1 is higher, so the image obtained using this band is brighter.