skip to main content

Title: Charged vanadium-benzene multidecker clusters: DFT and quantum Monte Carlo study

Using explicitly correlated fixed-node quantum Monte Carlo and density functional theory (DFT) methods, we study electronic properties, ground-state multiplets, ionization potentials, electron affinities, and low-energy fragmentation channels of charged half-sandwich and multidecker vanadium-benzene systems with up to 3 vanadium atoms, including both anions and cations. It is shown that, particularly in anions, electronic correlations play a crucial role; these effects are not systematically captured with any commonly used DFT functionals such as gradient corrected, hybrids, and range-separated hybrids. On the other hand, tightly bound cations can be described qualitatively by DFT. A comparison of DFT and quantum Monte Carlo provides an in-depth understanding of the electronic structure and properties of these correlated systems. The calculations also serve as a benchmark study of 3d molecular anions that require a balanced many-body description of correlations at both short- and long-range distances.
Authors:
;  [1] ;  [2] ;  [1] ;  [3]
  1. Institute of Physics, CCMS, Slovak Academy of Sciences, 84511 Bratislava (Slovakia)
  2. Department of Physics, North Carolina State University, Raleigh, North Carolina 27695-8202 (United States)
  3. (Slovakia)
Publication Date:
OSTI Identifier:
22493730
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 144; Journal Issue: 6; Other Information: (c) 2016 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; AFFINITY; ANIONS; ATOMS; BENCHMARKS; BENZENE; CAPTURE; CATIONS; COMPARATIVE EVALUATIONS; CORRELATIONS; DENSITY FUNCTIONAL METHOD; ELECTRONIC STRUCTURE; GROUND STATES; HYBRIDIZATION; IONIZATION POTENTIAL; MANY-BODY PROBLEM; MONTE CARLO METHOD; MULTIPLETS; VANADIUM