Structures and vibrational frequencies of vanadium (V) oligomers: An<i>ab initio</i>study using effective core potentials

Ribeiro‐Claro, Paulo J. A.; Amado, Ana M.; Teixeira‐Dias, J. J. C.

doi:10.1002/(sici)1096-987x(19960730)17:10<1183::aid-jcc1>3.0.co;2-k

Cited by 6 publications

(3 citation statements)

References 46 publications

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“…Our calculated distances for V···O would be expected to be too short because they correspond to double donor water molecules, for which the O···H–O angle deviates significantly from linearity. Our best Hartree–Fock and MP2 values of 1.708 and 1.796 Å can be compared with the best Hartree–Fock result reported in the work of Ribeiro–Claro (1.70 Å) as well as the B3LYP result of Rustad (1.740 Å) …”

Section: Resultsmentioning

confidence: 53%

Ab Initio Investigation of the Hydration of the Tetrahedral Perchlorate, Perbromate, Selenate, Arsenate, and Vanadate Anions

Pye

Walker

2011

J. Phys. Chem. A

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Section: Resultsmentioning

confidence: 53%

Ab Initio Investigation of the Hydration of the Tetrahedral Perchlorate, Perbromate, Selenate, Arsenate, and Vanadate Anions

Pye

Walker

2011

J. Phys. Chem. A

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“…Although computational studies of transition-metal [M 2 O 7 ] n - anions have concentrated on dichromate, − some calculations on the V, Nb, Ta, Mo, and W systems have been reported. ,, Considerable attention has been focused on the molecular structures of the oxoanions, as experimental data for crystals have revealed a diversity of conformations in the solid state. Also, investigations of the vibrational 12,16 and electronic 12 spectra of some species have been performed.…”

Section: Introductionmentioning

confidence: 99%

Structure and Bonding in Dinuclear Oxoanions of V, Nb, Ta, Mo, and W

Bridgeman

Cavigliasso

2001

J. Phys. Chem. A

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The structure and bonding in [M2O7] n - anions of the early transition metals V, Nb, Ta, Mo, and W have been investigated by density-functional methods. Several molecular conformations have been tested in geometry optimizations, and systems with a linear M−O−M bridge have been the only structures obtained for V, Nb, and Ta, and the most stable configurations for Mo and W. Molecular-orbital analysis has indicated that multiple bonds are formed between the metal and both bridging (Ob) and terminal (Ot) oxygen atoms. However, it has been found that M−Ob interactions are characterized by bond lengths and bond orders that are typical of a single M−O bond. The results from population analysis (Mulliken charges and Mayer bond indices) have suggested that the repulsive interactions between the ends of the molecules may be a more important structural factor in determining the configuration of the bridge than M−Ob π bonding is.

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“…Six, two, two, and two 1s functions are used for the 1s, 2s, 3s, and 4s atomic orbitals, respectively, four and two 2p functions are used for the 2p and 3p atomic orbitals, respectively, and four 3d functions for the 3d atomic orbitals. Addition of a d-type orbital with an exponent of 0.0885 on the vanadium atoms in this basis set significantly improves the representation of the vanadium atom . Not only is the augmented 12s, 6p, and 4d set more economical in integral evaluation but it also performs nearly as well as the augmented 12s, 6p, and 5d set in molecular applications.…”

Section: Methodsmentioning

confidence: 99%

Four- and Five-Coordinate Oxovanadium(V) Alkoxides: Do Steric Effects or Electronic Properties Dictate the Geometry?

1996

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Sterically hindered ligands generally form metal complexes with lower coordination numbers than less hindered ligands. In contrast to dogma, the solid state vanadium(V) complexes with ethylene glycol and pinacol contain four- and five-coordinate vanadium atoms, respectively. Ab initio and electrostatic potential distribution calculations were conducted on both experimental and optimized geometries of the four- and five-coordinate oxovanadium chloroalkoxides. Ab initio energy calculations favor the five-coordinate species for all ligands at all levels of theory examined. No significant differences in the electrostatic properties of the vanadium atoms in the two types of molecules were observed by using electrostatic potential distribution analysis. Methyl group substitutions on the ligand did not change the electronics of the vanadium atoms sufficiently to be a factor. Thus, we conclude that neither electronics nor sterics at the metal center explains the experimental geometries. In the absence of a significant observable electronic effect at the vanadium, we note that the experimental observations can be attributed to ligand geometric effects such as the Thorpe-Ingold and/or gem-dialkyl effects.

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Structures and vibrational frequencies of vanadium (V) oligomers: Anab initiostudy using effective core potentials

Cited by 6 publications

References 46 publications

Ab Initio Investigation of the Hydration of the Tetrahedral Perchlorate, Perbromate, Selenate, Arsenate, and Vanadate Anions

Ab Initio Investigation of the Hydration of the Tetrahedral Perchlorate, Perbromate, Selenate, Arsenate, and Vanadate Anions

Structure and Bonding in Dinuclear Oxoanions of V, Nb, Ta, Mo, and W

Four- and Five-Coordinate Oxovanadium(V) Alkoxides: Do Steric Effects or Electronic Properties Dictate the Geometry?

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