DOE OSTI2020
VO2 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are sixteen inequivalent V4+ sites. In the first V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three VO4 tetrahedra and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 1.72–2.19 Å. In the second V4+ site, V4+ is bonded to six O2- atoms to form distorted VO6 octahedra that share corners with three equivalent VO4 tetrahedra and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 1.71–2.28 Å. In the third V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three VO4 tetrahedra and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 1.75–2.13 Å. In the fourth V4+ site, V4+ is bonded to four O2- atoms to form corner-sharing VO4 tetrahedra. The corner-sharing octahedra tilt angles range from 49–56°. There are a spread of V–O bond distances ranging from 1.70–1.86 Å. In the fifth V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with four VO4 tetrahedra and edges with three VO6 octahedra. There are a spread of V–O bond distances ranging from 1.99–2.11 Å. In the sixth V4+ site, V4+ is bonded to four O2- atoms to form corner-sharing VO4 tetrahedra. The corner-sharing octahedra tilt angles range from 53–63°. There are a spread of V–O bond distances ranging from 1.79–1.98 Å. In the seventh V4+ site, V4+ is bonded to four O2- atoms to form corner-sharing VO4 tetrahedra. The corner-sharing octahedra tilt angles range from 45–55°. There are a spread of V–O bond distances ranging from 1.69–1.82 Å. In the eighth V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with four VO4 tetrahedra and edges with three VO6 octahedra. There are a spread of V–O bond distances ranging from 1.99–2.11 Å. In the ninth V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with six VO4 tetrahedra and edges with two equivalent VO6 octahedra. There are a spread of V–O bond distances ranging from 2.02–2.09 Å. In the tenth V4+ site, V4+ is bonded to four O2- atoms to form corner-sharing VO4 tetrahedra. The corner-sharing octahedra tilt angles range from 48–53°. There are a spread of V–O bond distances ranging from 1.70–1.84 Å. In the eleventh V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with six VO4 tetrahedra and edges with two equivalent VO6 octahedra. There are a spread of V–O bond distances ranging from 2.02–2.10 Å. In the twelfth V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with five VO4 tetrahedra and edges with three VO6 octahedra. There are a spread of V–O bond distances ranging from 2.00–2.16 Å. In the thirteenth V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with five VO4 tetrahedra and edges with three VO6 octahedra. There are a spread of V–O bond distances ranging from 1.71–2.13 Å. In the fourteenth V4+ site, V4+ is bonded to four O2- atoms to form corner-sharing VO4 tetrahedra. The corner-sharing octahedra tilt angles range from 47–58°. There are a spread of V–O bond distances ranging from 1.69–1.86 Å. In the fifteenth V4+ site, V4+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three equivalent VO4 tetrahedra and edges with four VO6 octahedra. There are a spread of V–O bond distances ranging from 1.72–2.20 Å. In the sixteenth V4+ site, V4+ is bonded to four O2- atoms to form corner-sharing VO4 tetrahedra. The corner-sharing octahedra tilt angles range from 53–62°. There are a spread of V–O bond distances ranging from 1.80–1.96 Å. There are thirty-two inequivalent O2- sites. In the first O2- site, O2- is bonded in a water-like geometry to two V4+ atoms. In the second O2- site, O2- is bonded in a water-like geometry to two V4+ atoms. In the third O2- site, O2- is bonded in an L-shaped geometry to two V4+ atoms. In the fourth O2- site, O2- is bonded in a distorted T-shaped geometry to three V4+ atoms. In the fifth O2- site, O2- is bonded in a distorted tetrahedral geometry to four V4+ atoms. In the sixth O2- site, O2- is bonded in a water-like geometry to two V4+ atoms. In the seventh O2- site, O2- is bonded in a distorted trigonal planar geometry to three V4+ atoms. In the eighth O2- site, O2- is bonded in a distorted trigonal planar geometry to three V4+ atoms. In the ninth O2- site, O2- is bonded in a water-like geometry to two V4+ atoms. In the tenth O2- site, O2- is bonded in a distorted trigonal planar geometry to three V4+ atoms. In the eleventh O2- site, O2- is bonded in a distorted T-shaped geometry to three V4+ atoms. In the twelfth O2- site, O2- is bonded in a distorted trigonal planar geometry to three V4+ atoms. In the thirteenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two V4+ atoms. In the fourteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to three V4+ atoms. In the fifteenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two V4+ atoms. In the sixteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to three V4+ atoms. In the seventeenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two V4+ atoms. In the eighteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to three V4+ atoms. In the nineteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to three V4+ atoms. In the twentieth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two V4+ atoms. In the twenty-first O2- site, O2- is bonded in a distorted trigonal planar geometry to three V4+ atoms. In the twenty-second O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two V4+ atoms. In the twenty-third O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two V4+ atoms. In the twenty-fourth O2- site, O2- is bonded in a water-like geometry to two V4+ atoms. In the twenty-fifth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to two V4+ atoms. In the twenty-sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to three V4+ atoms. In the twenty-seventh O2- site, O2- is bonded in a distorted trigonal planar geometry to three V4+ atoms. In the twenty-eighth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two V4+ atoms. In the twenty-ninth O2- site, O2- is bonded in a distorted trigonal pyramidal geometry to four V4+ atoms. In the thirtieth O2- site, O2- is bonded in a distorted trigonal planar geometry to three V4+ atoms. In the thirty-first O2- site, O2- is bonded in a distorted trigonal planar geometry to three V4+ atoms. In the thirty-second O2- site, O2- is bonded in a distorted trigonal planar geometry to three V4+ atoms.