Nuclear velocity perturbation theory for vibrational circular dichroism: An approach based on the exact factorization of the electron-nuclear wave function

Abstract

The nuclear velocity perturbation theory (NVPT) for vibrational circular dichroism (VCD) is derived from the exact factorization of the electron-nuclear wave function. This new formalism offers an exact starting point to include correction terms to the Born-Oppenheimer (BO) form of the molecular wave function, similarly to the complete-adiabatic approximation. The corrections depend on a small parameter that, in a classical treatment of the nuclei, is identified as the nuclear velocity. Apart from proposing a rigorous basis for the NVPT, we show that the rotational strengths, related to the intensity of the VCD signal, contain a new contribution beyond-BO that can be evaluated with the NVPT and that only arises when the exact factorization approach is employed. Numerical results are presented for chiral and non-chiral systems to test the validity of the approach.

arXiv comment13 pages, 5 figures, 4 tables

References in corpus (14)

• Phonons and related properties of extended systems from density-functional perturbation theory
• Exact factorization of the time-dependent electron-nuclear wavefunction
• Correlated electron-nuclear dynamics: Exact factorization of the molecular wavefunction
• A coupled-trajectory quantum-classical approach to decoherence in non-adiabatic processes
• Is the molecular Berry phase an artifact of the Born-Oppenheimer approximation?
• The exact forces on classical nuclei in non-adiabatic charge transfer
• Mixed quantum-classical dynamics from the exact decomposition of electron-nuclear motion
• Classical nuclear motion coupled to electronic non-adiabatic transitions
• Mixed quantum-classical dynamics on the exact time-dependent potential energy surface: A fresh look at non-adiabatic processes
• Reply to "Comment on 'Correlated electron-nuclear dynamics: Exact factorization of the molecular wavefunction' [J. Chem. Phys. 137, 22A530 (2012) ]''
• Comment on "Correlated electron-nuclear dynamics: Exact factorization of the molecular wavefunction" [J. Chem. Phys. 137, 22A530 (2012)]
• Semiclassical analysis of the electron-nuclear coupling in electronic non-adiabatic processes
• Laser-induced electron localization in H${}_2^{+}$: Mixed quantum-classical dynamics based on the exact time-dependent potential energy surface
• Exact Electronic Potentials in Coupled Electron-Ion Dynamics

Cited by in corpus (13)

• Light-Matter Interactions via the Exact Factorization Approach
• On the mass of atoms in molecules: Beyond the Born-Oppenheimer approximation
• The adiabatic limit of the exact factorization of the electron-nuclear wave function
• Ultrafast dynamics with the exact factorization
• An Exact Factorization Perspective on Quantum Interferences in Nonadiabatic Dynamics
• Bohmian mechanics in the exact factorization of electron-nuclear wavefunction
• Quantum-classical nonadiabatic dynamics of Floquet driven systems
• Representation and Conservation of Angular Momentum in the Born-Oppenheimer Theory of Polyatomic Molecules
• A Stern-Gerlach separator of chiral enantiomers based on the Casimir-Polder potential
• Non-adiabatic mass correction to the rovibrational states of molecules. Numerical application for the H${}_2^{+}$ molecular ion
• Electronic decoherence along a single nuclear trajectory
• Exactly factorized molecular Kohn-Sham density functional theory
• Rototranslational sum rules for nuclear dynamics via traveling pseudopotentials