Spin unrestricted linear scaling electronic structure theory and its application to magnetic carbon doped BN nanotubes

Abstract

We present an extension of density matrix based linear scaling electronic structure theory to incorporate spin degrees of freedom. When the spin multiplicity of the system can be predetermined, the generalization of the existing linear scaling methods to spin unrestricted cases is straightforward. However, without calculations it is hard to determine the spin multiplicity of some complex systems, such as, many magnetic nanostuctures, some inorganic or bioinorganic molecules. Here we give a general prescription to obtain the spin-unrestricted ground state of open shell systems. Our methods are implemented into the linear scaling trace-correcting density matrix purification algorithm. The numerical atomic orbital basis, rather than the commonly adopted Gaussian basis functions is used. The test systems include O2 molecule, and magnetic carbon doped BN(5,5) and BN(7,6) nanotubes. Using the newly developed method, we find the magnetic moments in carbon doped BN nanotubes couple antiferromagnetically with each other. Our results suggest that the linear scaling spin-unrestricted trace-correcting purification method is very powerful to treat large magnetic systems.