Extended basis NDDO calculations on diatomic molecules

The ab initio NDDO method as described by Roby has been investigated for a range of diatomic species, using symmetric orthonormalization and various basis set sizes. No limiting behaviour is observed with basis set extension.     

An optimum strategy for solution chemistry using semiempirical molecular orbital method: Importance of description of charge distribution

For the purpose to execute direct dynamics calculation in solution chemistry, we propose an optimum strategy for solution chemistry using semiempirical molecular orbital (MO) method with neglect of diatomic differential overlap (NDDO) approximation with specific solution reaction parameters (SSRP), i.e., the NDDO‐SSRP method. In this strategy, the empirical parameters of the semi‐empirical MO method were optimized individually for target molecule or ion by reference to the ab initio MO calculation data for many configurations on the potential energy surface near the reaction path. For demonstration, the NDDO‐SSRP method was applied to two molecules and two ions (OH^?, H₂O, NH₃, NH₄⁺) at their equilibrium states in aqueous solution, respectively. Accordingly, it was verified that both the potential energy surface and the charge distribution of these solutes in aqueous solution are dramatically improved to reproduce themselves accurately at ab initio MO calculation level. In conclusion, it is expected that the NDDO‐SSRP method should become quite useful for dynamic and statistical applications to chemical reaction systems in solution. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Comparison of NDDO and quasi-ab initio approaches to compute semiempirical molecular electrostatic potentials

The suitability of the two most widely used strategies to compute semiempirical MEPs is examined. For this purpose, MEP minima, electrostatic charges, and dipoles for a large number of molecules were computed at the AM1, MNDO, and PM3 levels using both the NDDO strategy developed by Ferenczy, Reynolds, and Richards and our own quasi-ab initio method. Results demonstrate that the quasi-ab initio is preferred over the NDDO method for the computation of MEP minima. It is also found that the best set of semiempirical charges and dipoles are obtained using either the AM1 NDDO or the MNDO quasi-ab initio methods. In these two cases, the quality of the results is fully comparable with 6-31G* values. © 1994 by John Wiley & Sons, Inc.     

The ab initio neglect of differential diatomic overlap method

The ab initio Neglect of Differential Diatomic Overlap (N.D.D.O.) method of Roby is tested numerically for an extensive series of molecules. Agreement with the full ab initio molecular orbital method is poor. Total energies are more negative and dipole moments are overestimated. The failings of the N.D.D.O. method are accounted for using multipole-multipole expansions.     

Theoretical conformational analysis of a simple sulphilimine model

The topomerization (bond rotation andS-pyramidal inversion) of a simple sulphilimine model, H₂SNH has been studied with the aid ofab initio SCF MO calculations. The highest rotation barrier occurs when the H₂SN moiety is planar, < HSN = 120 °. The maxima of the inversion crossections occur at the planar conformation for all rotation angles α as expected, however, the minima belong to different values when α is varied. The minimum energy path between the two lowest minima of the conformational energy surface consists of a pure inversion section and a section which is mostly rotation. The optimum values of the < HSN bond angles are significantly smaller than the corresponding < RSN bond angles of sulphilimines of bulkierR substituents.     

Chelation of carbocations by polyethers and polyamines

Chelates formed by carbocations and cyclic polyethers and polyamines are studied with semiempirical and ab initio MO methods.     

Comparative semiempirical and ab initio study of the harmonic vibrational frequencies of aniline—I. The ground state

The harmonic vibrational frequencies of the ground state S₀ of aniline obtained from various ab initio methods [6-31G, 6-31G(*) and 6-31G* basis sets] and semiempirical methods (MINDO/3, MNDO, AM1 and PM3) have been compared to the experimental vibrational spectra. Detailed theoretical analyses of the atomic Cartesian displacements of all normal modes are presented. The semiempirical PM3 method reproduces the experimental frequencies of aniline with comparable accuracy to the ab initio methods. Ale PM3 method will be useful in predicting the vibrational spectra of larger aromatic amines.     

Semiempirical NDDO calculations with STO-3G and 4-31G basis sets

Possible refinements of semiempirical methods include the use of larger basis sets and of correlated wave functions. These possibilities are investigated in semiempirical NDDO SCF calculations with the STO-3G and 4-31G basis sets, and in correlated calculations at the STO-3G level. The present approach is characterized by the analytical evaluation of all one-center terms and two-electron integrals, and the semiempirical adjustment of the remaining one-electron integrals and the nuclear repulsions. The NDDO SCF results tend to reproduce the correspondingab initio results more closely than experimental data, even if they are parametrized with respect to experiment. The explicit inclusion of electron correlation at the STO-3G level improves the calculated results only slightly.     

Vibrational and conformational analysis of n-propylamine by means of i.r. spectroscopy and ab initio MO calculations

The gas-phase i.r. absorption spectra of normal and amino-deuterated n-propylamine were observed. Most of the observed bands were assigned with the help of ab initio MO calculations for the normal frequencies. The ab initio force constants were scaled to fit the observed spectrum by a least squares method. The existence of five rotational isomers is suggested from an analysis of the NH₂ wagging and torsion bands. The gauche-conformers about the CN axis are found to occupy about 70 % of all n-propylamine molecules, and the gauche-conformers about the CC axis are found to be more abundant than the trans-conformers.     

Geometrical preferences of the crotyl anion,radical and cation

ab initio MO calculations have been performed on the cis and trans isomers of the crotyl cation, free radical and anion in each of two orientations of the Me rotor about the allylic framework. In agreement with available experimental data, both the crotyl cation and free radical prefer trans skeletal geometries. On the other hand, the cis isomer of the crotyl anion is found to be more stable than the trans, the same preference as has been noted for alkali metal allyl organometallics in solution, but opposite to that recently reported for the free (gas phase) anion. The Me groups are predicted to eclipse the partial double bond for the trans isomers of all three systems and for the cis cation. These results are rationalized with the aid of perturbation MO theory.     

Semiempirical treatment of electrostatic potentials and partial charges in combined quantum mechanical and molecular mechanical approaches

A semiempirical treatment of electrostatic potentials and partial charges is presented. These are the basic components needed for the evaluation of electrostatic interaction energies in combined quantum mechanical and molecular mechanical approaches. The procedure to compute electrostatic potentials uses AM1 and MNDO wave functions and is based on one previously suggested by Ford and Wang. It retains the NDDO approximation and is thus both easy to implement and computationally efficient. Partial atomic charges are derived from a semiempirical charge equilibration model, which is based on the principle of electronegativity equalization. Large sets of ab initio restricted Hartee-Fock (RHF/6-31G*) reference data have been used to calibrate the semiempirical models. Applying the final parameters (C, H, N, O), the ab initio electrostatic potentials are reproduced with an average accuracy of 20% (AM1) and 25% (MNDO), respectively, and the ab initio potential derived charges normally to within 0.1 e. In most cases our parameterized models are more accurate than the much more expensive quasi ab initio techniques, which employ deorthogonalized semiempirical wave functions and have generally been preferred in previous applications. © 1996 John Wiley & Sons, Inc.     

A theoretical investigation of the rotational barriers of peroxyformic acid

The internal rotational barriers in peroxyformic acid have been studied employing ab initio MO calculations. The C-O and O-O rotational barriers were calculated to be 7.68 and 1.04 $\text{kcal}\text{mol}$, respectively. The relatively low O-O rotational barrier is attributed to a balance between electron repulsion and hydrogen bonding in the syn chelated conformer.     

Das SCF–MO–P(LCGO)-Verfahren und seine Varianten

A modification of the SCF –MO –LCGO method is proposed in the form of a qualitative ab initio method. Naphthalene is treated as a test case; good agreement between calculated and experiemental results is obtained. The capabilities of the method for quantum-chemical calculations are discussed.     

NDDO MO calculations

Three valence-only schemes based on the Roby version of NDDO MO theory, which differ only in the core-valence treatment and the choice of the basis set, have been applied to the study of molecules containing first-row atoms. Orbital energies, charge distribution, dipole moments, field gradients, and a few other one-electron molecular properties are calculated to satisfactory accuracy. The schemes appear unreliable in the prediction of barriers to internal rotation in molecules, presumably due to errors in the core contribution to the total energy. An alternative treatment is suggested.     

Chlorosilanes: Development and application of MM2 force field parameters

The geometries, relative conformational energies, and dipole moments of mono and polychlorosilanes have been calculated using ab initio molecular orbital (MO) theory. Calculations at the HF/3–21G(*) level, with the exception of dipole moments, give reasonable agreement with experimental data. A new MM2 force field for chlorosilanes, which includes terms for bond length shortening and bond angle compression due to the attachment of electronegative Cl atoms, has been developed on the basis of experimental and ab initio results. The new force field is generally successful in predicting structural parameters, but is unable to reproduce the dipole moments of several model systems. While dipole moment predictions are not the authors' main interest, this failure defines a shortcoming in the MM2 method. The new parameters have been applied to problems in the prediction of stereochemistries of cyclic systems, and compared with experimental results where data are available.     

Theoretical studies of d-d and d-π-d magnetic interactions in (EDT-TTFVO)2FeBr4 crystals

The effective exchange integrals (J(HB)) of the Heisenberg spin model have been evaluated by using the ab initio MO and based on Hartree-Fock (HF) and density functional theory (DFT) for organic magnetic metals, the (EDT-TTFVO)₂FeBr₄ crystal based on the X-ray crystallographic structures at 113 K. In order to study the magnetic properties, we proposed some of the pairs, where the direct (d-d) and indirect (d-π-d) magnetic couplings between Fe(III) d-spins (S = 5/2) without/with π-dimer spins (S = 1/2) were calculated, respectively. The effective exchange integrals were evaluated by using UB3LYP method, and principal J values were 0.5, −0.1 and 0.4 K. From these results, it is found that there were three dimensional spin arrangements of Fe(III) d-spins. The Quantum Monte Carlo (QMC) simulations had been carried out with our calculated J values to evaluate the magnetic susceptibility for this molecular crystal, reproducing the experimental tendency.     

NDDO MO calculations: isotropic hyperfine coupling constants and nuclear spin-spin coupling constants

The nonempirical NDDO MO method in its unrestricted form has been used to evaluate isotropic hyperfine coupling constants and nuclear spin-spin coupling constants. Satisfactory agreement with INDO and experimental results is obtained.     

A comparative study of approximate SCF MO treatments of hydrides

A comparative study of approximate and exact ab initio treatments of H₂O, NH₃ and CH₄ has been carried out. Three approximate schemes based on the NDDO approach are introduced. The results compare well with best results obtained by other authors.

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Zusammenfassung Die angenäherte und exakte ab initio Behandlung von H₂O, NH₃ and CH₄ wird verglichen. Drei Verfahren, die auf die NDDO-Näherung zurückgehen, werden eingeführt. Die Resultate sind von vergleichbarer Qualität wie die besten Ergebnisse anderer Autoren.

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The work was partly supported by the Institute of Low Temperatures of the Polish Academy of Sciences, Wrocaw.