Research outline

We develop theoretical methods and computer programs for studying electronic structure, physical properties, and chemical reactions of molecules and solids. The focus of our research is on the Kohn–Sham density-functional method, particularly on designing new density-functional approximations in the form of model Kohn–Sham potentials. Another theme is development of new techniques for solving the Schrödinger equation for interacting electrons confined to cavities of irregular shape. We also use computational chemistry methods to solve practical problems of chemistry and spectroscopy.

  I. Density-functional theory

Potential-driven density-functional theory is a version of the Kohn–Sham scheme in which one directly approximates ("models") the exchange-correlation potential rather than the corresponding energy functional. This approach has a number of attractive features, but has long remained underexplored because of perceived methodological difficulties. Over the past few years, we have made significant progress in reviving and advancing this method.

      Representative publications:

• "Explicit construction of functional derivatives in potential-driven density-functional theory," A. P. Gaiduk and V. N. Staroverov, J. Chem. Phys. 133, 101104 (2010).

• "Reconstruction of density functionals from Kohn–Sham potentials by integration along density scaling paths," A. P. Gaiduk, S. K. Chulkov, and V. N. Staroverov, J. Chem. Theory Comput. 5, 699 (2009).

• "A family of model Kohn–Sham potentials for exact exchange," V. N. Staroverov, J. Chem. Phys. 129, 134103 (2008).

  II. Spatially confined few-electron systems

We have developed a near-exact general method for solving the Schrödinger equation for one or two electrons in almost any axially symmetric cavity (e.g., a cylinder, an ellipsoid, a bulged cylinder). Using this method for a pair of interacting electrons in a model dogbone-shaped cavity we were able to explain the experimentally observed relationship between magnetic coupling constants and geometric parameters of intercavity channels in electrides.

      Representative publications:

• "Solution of the Schrödinger equation for two electrons in axially symmetric cavities," I. G. Ryabinkin and V. N. Staroverov, Phys. Rev. A 82, 022505 (2010).

• "Two electrons in a cylindrical box: An exact configuration-interaction solution," I. G. Ryabinkin and V. N. Staroverov, Phys. Rev. A 81, 032509 (2010).

  III. Computational chemistry

Applied computational research in our group centers on elucidating the mechanisms of chemical reactions, understanding the electronic structure of electrides, and unraveling the intricacies of chemical bonding in compounds under high pressure.

      Representative publications:

• "A cryptand-encapsulated germanium(II) dication," P. A. Rupar, V. N. Staroverov, and K. M. Baines, Science 322, 1360 (2008).

• "Photodissociation of the geometric isomers of 1,2-dibromoethylene," W. Shi, V. N. Staroverov, and R. H. Lipson, J. Chem. Phys. 131, 154304 (2009).