Characterization of an F‐center in an alkali halide cluster

The removal of a fluorine atom from its central position in a cubiclike Li14F13+ cluster creates an F‐center vacancy that may or may not be occupied by the remaining odd electron. The topology exhibited by the electron density in Li14F12+, the F‐center cluster, enables one to make a clear distinction between the two possible forms that the odd electron can assume. If it possesses a separate identity, then a local maximum in the electron density will be found within the vacancy and the F‐center will behave quantum mechanically as an open system, bounded by a surface of local zero flux in the gradient vector field of the electron density. If, however, the density of the odd electron is primarily delocalized onto the neighboring ions, then a cage critical point, a local minimum in the density, will be found at the center of the vacancy. Without an associated local maximum, the vacancy has no boundary and is undefined. Self‐consistent field (SCF) calculations with geometry optimization of the Li14F13+ cluster...

[1]  Hanno Essén,et al.  The characterization of atomic interactions , 1984 .

[2]  M. Wagner,et al.  ALKALIDES, ELECTRIDES, AND EXPANDED METALS , 1993 .

[3]  Á. M. Pendás,et al.  Ions in crystals: The topology of the electron density in ionic materials. I. Fundamentals , 1997 .

[4]  Á. M. Pendás,et al.  Ions in crystals: The topology of the electron density in ionic materials.II. The cubic alkali halide perovskites , 1997 .

[5]  C. Gatti,et al.  Total electronic charge density of L-alanine from X-ray diffraction at 23 K , 1991 .

[6]  R. Bader,et al.  On the presence of non-nuclear attractors in the charge distributions of Li and Na clusters , 1987 .

[7]  R. Bader,et al.  Properties of atoms in molecules : magnetic susceptibilities , 1993 .

[8]  M. Sakata,et al.  Accurate structure analysis by the maximum‐entropy method , 1990 .

[9]  D. Pooley,et al.  F Band Absorption in Alkali Halides as a Function of Temperature , 1969 .

[10]  W. B. Fowler,et al.  Physics of color centers , 1968 .

[11]  R. Bader.  Atoms in molecules : a quantum theory , 1990 .

[12]  Cheng Chang,et al.  Properties of atoms in molecules: atomic volumes , 1987 .

[13]  R. Bader,et al.  A topological theory of molecular structure , 1981 .

[14]  C. Kittel.  Introduction to solid state physics , 1954 .

[15]  R. Bader,et al.  An atomic population as the expectation value of a quantum observable , 1992 .

[16]  R. Bader,et al.  Theoretical analysis of hydrocarbon properties. 2. Additivity of group properties and the origin of strain energy , 1987 .

[17]  P. F. Zhou,et al.  Topological definition of crystal structure: determination of the bonded interactions in solid molecular chlorine , 1995 .

[18]  R. Bader,et al.  Spatial localization of the electronic pair and number distributions in molecules , 1975 .

[19]  B. Iversen,et al.  Experimental evidence for the existence of non-nuclear maxima in the electron-density distribution of metallic beryllium. A comparative study of the maximum entropy method and the multipole refinement method. , 1995, Acta crystallographica. Section B, Structural science.

[20]  Todd A. Keith,et al.  Topological analysis of magnetically induced molecular current distributions , 1993 .

[21]  Friedrich Biegler-König,et al.  Calculation of the average properties of atoms in molecules. II , 1982 .

[22]  W. Holton,et al.  Paramagnetic Resonance of F Centers in Alkali Halides , 1962 .

[23]  David J. Singh,et al.  Theoretical determination that electrons act as anions in the electride Cs+ (15-crown-5)2·e- , 1993, Nature.

[24]  R. Bader,et al.  Use of electron charge and current distributions in the determination of atomic contributions to magnetic properties , 1996 .

[25]  F. C. Brown,et al.  Faraday rotation of the K band in RbCl , 1965 .

[26]  K. Edgecombe,et al.  Topological analysis of the charge density of solids: bcc sodium and lithium , 1993 .

[27]  R. Bader,et al.  Virial Field Relationship for Molecular Charge Distributions and the Spatial Partitioning of Molecular Properties , 1972 .

[28]  Todd A. Keith,et al.  Properties of atoms in molecules: additivity and transferability of group polarizabilities , 1992 .

[29]  A. J. Duke,et al.  Quantum topology of molecular charge distributions. 1 , 1979 .

[30]  R. Bader,et al.  A topological definition of a Wigner–Seitz cell and the atomic scattering factor , 1994 .

[31]  G. G. Hall,et al.  Orthogonal trajectories of the electron density , 1977 .

[32]  G. A. Jeffrey,et al.  The Application of Charge Density Research to Chemistry and Drug Design , 1991 .

[33]  M. Eberhart,et al.  Bonding-property relationships in intermetallic alloys , 1993 .

[34]  J. Tennyson,et al.  A study of the variational convergence of the F centre energy levels of LiF , 1981 .

[35]  J. Platts,et al.  Periodic Hartree–Fock calculations on crystalline HCN , 1996 .

[36]  N. Kosugi,et al.  An Ab Initio Molecular Orbital Approach to Electronic Structures of the F Center in NaCl. Effects of Basis Set and Cluster Size , 1993 .

[37]  David Y. Smith.  THEORY OF SPIN-ORBIT EFFECTS IN THE F BAND IN ALKALI HALIDES , 1965 .

[38]  R. Bader.  Chemistry and the near‐sighted nature of the one‐electron density matrix , 1995 .

[39]  Michael B. Hursthouse,et al.  Experimental and theoretical study of the charge density in 2‐methyl‐4‐nitroaniline , 1992 .

[40]  P. Roversi,et al.  Charge density in crystalline citrinin from X-ray diffraction at 19 K , 1996 .

[41]  J. W. Downs,et al.  The Laplacian of the electron density and the electrostatic potential of danburite, CaB2Si2O8 , 1992 .

[42]  Paul L. A. Popelier,et al.  The electron pair , 1996 .

[43]  R. Bader,et al.  Structural homeomorphism between the electron density and the virial field , 1996 .

[44]  G. Pacchioni,et al.  Charge density topological study of bonding in lithium clusters , 1987 .

[45]  R. Bader,et al.  Quantum topology of molecular charge distributions. II. Molecular structure and its change , 1979 .

[46]  R. Bader,et al.  Properties of atoms in molecules: nuclear magnetic shielding , 1996 .

[47]  Báder.  Principle of stationary action and the definition of a proper open system. , 1994, Physical review. B, Condensed matter.