First-principles calculation of the optical rotatory power of periodic systems: Modern theory with modern functionals

An analysis of orbital magnetization in insulators is provided. It is shown that a previously proposed electronic orbital angular-momentum operator generalizes the "modern theory of orbital magnetization" to include nonlocal Hamiltonians. Expressions for magnetic transition dipole moments needed for the calculation of optical rotation and other properties are developed. A variety of issues that arise in this context are critically analyzed. These issues include periodicity of the operators, previously proposed band dispersion terms, and, if and where needed, evaluation of reciprocal space derivatives of orbital coefficients. Our treatment is used to determine the optical rotatory power of insulators employing a formulation that accounts for electric dipole-electric quadrupole (DQ), as well as electric dipole-magnetic dipole, contributions. An implementation in the public CRYSTAL program is validated against a model finite system and applied to the & alpha;-quartz mineral through linear-response timedependent density functional theory with a hybrid functional. The latter calculations confirmed the importance of DQ terms. Agreement against experiment was only possible with (i) use of a high-quality basis set, (ii) inclusion of a fraction of nonlocal Fock exchange, and (iii) account of orbital-relaxation terms in the calculation of response functions.