Relativistic formalism of nonadiabatic electron-nucleus-radiation dynamics in molecules: Path-integral approach

Abstract

Many-electron relativistic quantum theories of stationary molecular electronic states have been developed in so-called quantum chemistry, in which nuclear configuration is frozen in space-time under the Born-Oppenheimer approximation. These time-independent methods are concerned with energetics, which are supposed to determine molecular structures and dominate low-energy chemical reactions. Yet, rapid progress in laser technology demands that theoretical chemistry should get prepared for relativistic electron-nucleus coupled dynamics driven by unconventional ultrastrong laser pulses. We therefore generalize our previously developed path-integral formalism of nonadiabatic electron dynamics [Hanasaki and Takatsuka, Phys. Rev. A 81, 052514 (2010)] to cover the relativistic regime in radiation fields. Starting from a formal relativistic path-integral formulation of electron-nucleus coupled systems interacting with quantum radiation fields, we reduce it to a tractable level of approximations to set a theoretical foundation for future applications.