Decay rate of real space delocalization measures: a comparison between analytical and test systems

Literature Information

Publication Date 2016-01-08
DOI 10.1039/C5CP06098B
Impact Factor 3.676
Authors

A. Gallo-Bueno, E. Francisco, A. Martín Pendás


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Abstract

We examine in this contribution the possible relation between the spatial decay rate of real space delocalization measures and the insulating- or metallic-like character of molecular and extended systems. We first show that in simple one-electron models, like the Hückel or tight binding approximations, delocalization indices (DIs) are intimately linked to the first-order reduced density matrix (1RDM), whose decay rate is known to be exponential in gapped systems and algebraic in gapless ones. DIs are shown to behave equivalently, with wild oscillations in gapless 1D, 2D and 3D models that do only persist in one-dimensional real cases, as computed at the Hartree–Fock or Kohn–Sham levels. Oscillations are shown to be directly related to Pauling resonant structures and chemical mesomerism. DIs in insulating-like moieties decay extremely fast. We propose that examining the decay of DIs along different directions in real materials may be used to detect facile and non-facile conductivity channels.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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