First principles nuclear magnetic resonance signatures of graphene oxide

Nuclear magnetic resonance (NMR) has been widely used in graphene oxide (GO) structure studies. However, the detailed relationship between its spectroscopic features and the GO structural configuration remains elusive. Based on first principles $C13$ chemical shift calculations using the gauge including projector augmented waves method, we provide a reliable spectrum-structure connection. The $C13$ chemical shift in GO is found to be very sensitive to the atomic environment, even for the same type of oxidation groups. Factors determining the chemical shifts of epoxy and hydroxy groups have been discussed. GO structures previously reported in the literature have been checked from the NMR point of view. The energetically favorable hydroxy chain structure is not expected to be widely existed in real GO samples according to our NMR simulations. The epoxy pair species we proposed previously is also supported by chemical shift calculations.