A relativistic Kohn–Sham density functional procedure by means of direct perturbation theory

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Abstract
The direct perturbation theory of relativistic effects is applied to the Kohn–Sham density functional procedure. The relativistic correction to the total energy is calculated through the leading order. A method for the determination of analytic energy derivatives of the resulting total energy expression is presented, which allows the calculation of the relativistic correction to molecular forces and other first‐order properties like e.g. the dipole moment. The method is applied to the diatomic ‘‘benchmark’’ molecules AgH, AuH, and Au2, and to the transition metal carbonyls Mo(CO)6, Pd(CO)4, and W(CO)6.