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

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, similar 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.
Authors:
 [1] ;  [2] ;  [2] ; ;  [3] ;  [1] ;  [4] ;  [2]
  1. Martin-Luther-University Halle-Wittenberg, von-Danckelmann-Platz 4, D-06120 Halle (Germany)
  2. (France)
  3. Max-Planck-Institute of Microstructure Physics, Weinberg 2, D-06120 Halle (Germany)
  4. UMR 8640 ENS-CNRS-UPMC, Département de Chimie, 24 rue Lhomond, École Normale Supérieure, 75005 Paris (France)
Publication Date:
OSTI Identifier:
22493531
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 7; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ADIABATIC APPROXIMATION; BORN-OPPENHEIMER APPROXIMATION; CHIRALITY; CORRECTIONS; DICHROISM; ELECTRONS; FACTORIZATION; PERTURBATION THEORY; VELOCITY; WAVE FUNCTIONS