Ab initio SCF calculations for azulene and naphthalene

doi:10.1016/0009-2614(69)80014-X

Chemical Physics Letters

Volume 3, Issue 1, January 1969, Pages 37-42

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Abstract

Ab initio SCF MO calculations for the C₁₀H₈ isomers azulene and naphthalene have been carried out using a basis set of gaussian expansions of near Hartree-Fock AO's. Ionization potentials, bond orders and charge densities for the ground and two doubly excited states of these molecules are discussed.

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AM1 calculations with complete optimization have been carried out on the azulene molecule and its derivatives such as 1-aza-azulene and 1,3-diaza-azulene. We show that AM1 is an appropriate method for predicting the structure and energy properties of azulene. Experimental values are found with good accuracy and computer results are analogous to those obtained by sophisticated methods such as the ab initio method (6-31G^∗). We describe a complete theoretical study of the structural and energy properties of 1-aza-azulene and 1,3-diaza-azulene in their ground states using the same method with full geometry optimization. From the theoretical finding, the most stable conformations are proposed. Otherwise, these geometrical conformations are preserved in order to determine some spectroscopic values of these compounds using the CNDO/M method. Our results are in qualitative agreement with the experimental data.
Ab initio study of the structure and dipole moment of azulene
1993, Chemical Physics Letters
The two structures of azulene with C_2v and C_s symmetry, their energy difference and their dipole moments have been investigated via ab initio quantum mechanics. Self-consistent-field (SCF) theory was used in conjunction with various basis sets up to TZP+f quality. The SCF method fails to predict the correct minimum energy structure (C_s instead of C_2v) due to the neglect of electron correlation. MP2 wavefunctions were used to analyze different correlation contributions which reduce the SCF value of the dipole moment μ by ≈ 0.5 D. The application of the MR-SDCI method yields μ = 0.93 D in good agreement with the experimental value (μ_exp = 0.79 D). The results are discussed by means of perturbation theory. Additionally, the azulene “sandwich” dimer was investigated at several internuclear distances to explore the origin of the disordered crystal structure.
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Ab initio SCF calculations for azulene and naphthalene

Abstract

J. Mol. Spectry.

J. Mol. Spectry.

Tetrahedron

J. Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

Acta Cryst.