Noble gas catalysed 1,2-migrations in N2H+ and N2CH3+

1998 ◽  
Vol 76 (8) ◽  
pp. 1138-1143 ◽  
Author(s):  
Alwin Cunje ◽  
Christopher F Rodriquez ◽  
Diethard K Bohme ◽  
Alan C Hopkinson
Keyword(s):  
Molecular Orbital ◽  
Noble Gas ◽  
Single Point ◽  
Molecular Orbital Calculations ◽  
Molecular Orbital Theory ◽  
Orbital Theory ◽  
Transition Structures ◽  
Uncatalysed Reaction

Molecular orbital calculations are reported for N2H+ and N2CH3+ and for the transition structures for the rearrangement of these ions by 1,2-shifts of H and CH3. All reaction profiles were also calculated with one atom of noble gas, M, present (M = Ne, Ar, Kr). Structure optimizations were performed at B3LYP/6-311++G(d,p) and, in the case of N2H+···M, single point calculations were also performed at QCISD(T)(full)/6-311++G(2df,p). For N2H+, inclusion of one noble gas atom reduces the barrier to rearrangement from 46.6 kcal mol-1 for the uncatalysed reaction to 42.6 kcal mol-1 (by Ne), to 21.4 kcal mol-1 (by Ar), and to 11.0 kcal mol-1 (by Kr). For N2CH3+, the barrier of 36.4 kcal mol-1 is reduced to 35.1 kcal mol-1 by Ne, to 27.4 kcal mol-1 by Ar, and to 18.4 kcal mol-1 by Kr.Key words: catalysis, molecular orbital theory, argon, krypton.

CNDO–MO Study of the Ozonide Ion and Related Species

1973 ◽  
Vol 51 (13) ◽  
pp. 2124-2128 ◽  
Author(s):  
John M. Sichel
Keyword(s):  
Molecular Orbital ◽  
Unpaired Electron ◽  
Related Species ◽  
Bond Angle ◽  
Molecular Orbital Calculations ◽  
Molecular Orbital Theory ◽  
Orbital Theory ◽  
Exchange Effect ◽  
Cndo Approximation ◽  
Extra Electron

The unpaired electron in the ozonide ion (O3−) is expected to occupy an antibonding molecular orbital; yet published experimental results indicate a shorter bond length and larger force constants than in neutral ozone. Molecular orbital calculations in the CNDO approximation are reported for this ion and related species (O3, SO2, SO2−, OF2+, OF2), using both the CNDO/2 and CNDO/BW parametrizations. Both methods predict that the bond lengths in O3− are 0.04 Å longer than in O3, in agreement with qualitative molecular orbital theory, and that the bond angle is 1° less than in O3. The CNDO/BW method predicts that the electron affinity of O3 is higher than that of the O atom, in agreement with experiment, since a stabilizing exchange effect outweighs the antibonding nature of the orbital occupied by the extra electron.

An abinitio molecular orbital study of isomers on the C2NH5+• and C2NH5 surfaces

1984 ◽  
Vol 62 (5) ◽  
pp. 922-925 ◽  
Author(s):  
Min H. Lien ◽  
Alan C. Hopkinson
Keyword(s):  
Molecular Orbital ◽  
Single Point ◽  
Radical Cations ◽  
Basis Set ◽  
Molecular Orbital Theory ◽  
Orbital Theory ◽  
Hartree Fock ◽  
Theory Structure ◽  
Molecular Orbital Study ◽  
Orbital Study

The structures and relative energies of seven possible C2NH5+•isomers have been calculated using abinitio molecular orbital theory. Structure optimisations have been performed with a 4-31G basis set, using both the restricted (RHF) and unrestricted (UHF) Hartree–Fock methods. The optimum geometries were then used for single point calculations using the 6-31G* basis set. The relative energies are 1 < 7 < 5 < 3 ≈ 2 ≈ 6 < 4. This order is the same, with the exception of 6, as for isomers on the C2H4O+•surface and the relative energies are very similar to those on the C2H4O+• surface. The structures of the radical cations C2NH5+• are compared with those of the neutral molecules C2NH5.

Bonding in Transition Metal Silyl Dimers. Molecular Orbital Theory

1989 ◽  
Author(s):  
Alfred B. Anderson ◽  
Paul Shiller ◽  
Eugene A. Zarate ◽  
Claire A. Tessier-Youngs ◽  
Wiley J. Youngs
Keyword(s):  
Transition Metal ◽  
Molecular Orbital ◽  
Molecular Orbital Theory ◽  
Orbital Theory

Approximate molecular orbital theory for inorganic molecules

1970 ◽  
Vol 16 (4) ◽  
pp. 291-302 ◽  
Author(s):  
R. D. Brown ◽  
K. R. Roby
Keyword(s):  
Molecular Orbital ◽  
Molecular Orbital Theory ◽  
Orbital Theory ◽  
Inorganic Molecules

Interpretation of experimental M�ssbauer quadrupole splittings of iron pentacyanide complexes using molecular orbital theory

1974 ◽  
Vol 35 (3) ◽  
pp. 231-236 ◽  
Author(s):  
Alfred Trautwein ◽  
Frank E. Harris ◽  
Istvan D�zsi
Keyword(s):  
Molecular Orbital ◽  
Molecular Orbital Theory ◽  
Orbital Theory
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