Charged vanadium-benzene multidecker clusters: DFT and quantum Monte Carlo study
- Institute of Physics, CCMS, Slovak Academy of Sciences, 84511 Bratislava (Slovakia)
- Department of Physics, North Carolina State University, Raleigh, North Carolina 27695-8202 (United States)
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.
- OSTI ID:
- 22493730
- Journal Information:
- Journal of Chemical Physics, Vol. 144, Issue 6; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
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