skip to main content

Title: Molecular quantum mechanical gradients within the polarizable embedding approach—Application to the internal vibrational Stark shift of acetophenone

We present an implementation of analytical quantum mechanical molecular gradients within the polarizable embedding (PE) model to allow for efficient geometry optimizations and vibrational analysis of molecules embedded in large, geometrically frozen environments. We consider a variational ansatz for the quantum region, covering (multiconfigurational) self-consistent-field and Kohn–Sham density functional theory. As the first application of the implementation, we consider the internal vibrational Stark effect of the C=O group of acetophenone in different solvents and derive its vibrational linear Stark tuning rate using harmonic frequencies calculated from analytical gradients and computed local electric fields. Comparisons to PE calculations employing an enlarged quantum region as well as to a non-polarizable embedding scheme show that the inclusion of mutual polarization between acetophenone and water is essential in order to capture the structural modifications and the associated frequency shifts observed in water. For more apolar solvents, a proper description of dispersion and exchange–repulsion becomes increasingly important, and the quality of the optimized structures relies to a larger extent on the quality of the Lennard-Jones parameters.
Authors:
; ;  [1] ; ; ;  [2] ;  [1] ;  [3]
  1. Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, Odense M, Odense DK-5230 Denmark (Denmark)
  2. Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø–The Arctic University of Norway, N-9037 Tromsø (Norway)
  3. (Switzerland)
Publication Date:
OSTI Identifier:
22416008
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 3; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACETOPHENONE; CAPTURE; COMPARATIVE EVALUATIONS; DENSITY FUNCTIONAL METHOD; ELECTRIC FIELDS; IMPLEMENTATION; MODIFICATIONS; MOLECULES; OPTIMIZATION; POLARIZATION; QUANTUM MECHANICS; SELF-CONSISTENT FIELD; SOLVENTS; STARK EFFECT; WATER