<scp>NDDO</scp>/<scp>MC</scp>: A new semiempirical <scp>SCF</scp><scp>MO</scp> method for transition metal complexes

Filatov, Michael; Zilberberg, Igor L.; Zhidomirov, G. M.

doi:10.1002/qua.560440414

Cited by 38 publications

(23 citation statements)

References 46 publications

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“…In this work all calculations have been performed in the cluster approximation using NDDO/MC semiempirical Hamiltonian [8]. The NDDO/MC method is based on the approximation of zero diatomic differential overlap which results in neglecting of 3-, 4-and part of 2-center two-electron integrals to be appeared in the Fock matrix [10].…”

Section: Methodsmentioning

confidence: 99%

“…The aim of this work is to obtain some insight into the process of the NACs adsorption on the metal iron by means of the Neglect of Diatomic Differential Overlap for Metal Compounds (NDDO/MC) semi-empirical method [8]. This method has been parameterized to reproduce the experimental geometry and binding energy for molecules like HNO, HNO 2 , FeO and FeN2 [9].…”

Section: Introductionmentioning

confidence: 99%

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Reduction of Nitroaromatic Compounds on the Surface of Metallic Iron: Quantum Chemical Study

Zilberberg

Pelmenschikov

McGrath

et al. 2002

IJMS

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Abstract:The initial reduction steps of nitroaromatic compounds on the surface of metallic iron have been studied theoretically using nitrobenzene (NB) as a representative of nitroaromatic compounds. The quantum chemical cluster approximation within the semiempirical Neglect of Diatomic Differential Overlap for Metal Compounds method was applied to model the Fe(110) crystallographic surface, taken as a representative reactive surface for granular iron. This surface was modeled as a 39-atom two-layer metal cluster with rigid geometry. The associative and dissociative adsorption of nitrobenzene was considered. Based on our quantum chemical analysis, we suggest that the direct electron donation from the metal surface into the π * orbital of NB is a decisive factor responsible for subsequent transformation of the nitro group. Molecularly adsorbed NB interacts with metal iron exclusively through nitro moiety oxygens which occupy tri-coordinated positions on surface The charge transfer from metal to NB of approximately 2 atomic units destablizes the nitro group. As a result, the first dissociation of the N-O bond goes through a relatively low activation barrier. The adsorbed nitrosobenzene is predicted to be a stable surface species, though still quiet labile.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Reduction of Nitroaromatic Compounds on the Surface of Metallic Iron: Quantum Chemical Study

Zilberberg

Pelmenschikov

McGrath

et al. 2002

IJMS

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“…The inclusion of systems with strong electron correlation in

scriptD

may lead to a bias in p which would at least partially explain the generally poor accuracy for transition‐metal complexes. Despite significant efforts, it was not yet possible to create an NDDO‐SEMO model which achieves a similar accuracy with respect to the reference data for transition‐metal complexes as for organic compounds …”

Section: Implicit Description Of Electron Correlation Effects Throughmentioning

confidence: 99%

Semiempirical molecular orbital models based on the neglect of diatomic differential overlap approximation

Husch

Vaucher

Reiher

2018

Int J of Quantum Chemistry

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Semiempirical molecular orbital (SEMO) models based on the neglect of diatomic differential overlap (NDDO) approximation efficiently solve the self-consistent field equations by rather drastic approximations. The computational efficiency comes at the cost of an error in the electron-electron repulsion integrals. The error may be compensated by the introduction of parametric expressions to evaluate the electron-electron repulsion integrals, the one-electron integrals, and the core-core repulsion. We review the resulting formalisms of popular NDDO-SEMO models (such as the MNDO(/d), AM1, PMx, and OMx models) in a concise and self-contained manner. We discuss the approaches to implicitly and explicitly describe electron correlation effects within NDDO-SEMO models and we dissect strengths and weaknesses of the different approaches in a detailed analysis. For this purpose, we consider the results of recent benchmark studies. Furthermore, we apply bootstrapping to perform a sensitivity analysis for a selection of parameters in the MNDO model. We also identify systematic limitations of NDDO-SEMO models by drawing on an analogy to Kohn-Sham density functional theory. K E Y W O R D SNDDO approximation, semi-empirical methods | INTRODUCTIONThe driving force for the development of semiempirical molecular orbital (SEMO) models has always been the desire to accelerate quantum chemical calculations. At the outset of the development of SEMO models in the middle of the last century, [1][2][3][4][5][6][7][8][9][10] the goal was to carry out electronic structure calculations for small molecules, which was not routinely possible with ab initio electronic structure methods at that time. Since then, theoretical chemistry has seen a remarkable development not only in terms of computational resources but also in terms of ab initio methodology. [11] One must not forget that most electronic structure methods which we apply routinely today, such as Kohn-Sham density functional theory (KS-DFT) [12] and coupled cluster theory, [13] were developed concurrently with today's SEMO models. As a consequence of algorithmic and methodological developments, [11] accurate ab initio electronic structure methods have long replaced SEMO models in their original areas of application (electronic structure calculations for small molecules). Nevertheless, SEMO models did not become extinct. Instead, they opened up different areas of application which can broadly be divided into three categories (see also Ref. [14] for a recent review): (1) simulations of very large systems such as proteins [15][16][17][18][19][20][21][22] and those with thousands of small molecules, [23,24] (2) calculations for a large number of isolated and unrelated medium-sized molecules, for example, in virtual high-throughput screening schemes for materials discovery [25,26] and docking-and-scoring of potential drug candidates, [27][28][29][30][31][32] and (3) entirely new applications such as real-time quantum chemistry where ultra-fast SEMO models allow the perception of visual and h...

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“…1 This method is still successfully used for the interpretation of optical spectra. Later, other methods based on the NDDO approximation 2,3 and the CNDO approximation 4 were modified for calculations including 3d orbitals. More recently, the popular semiempirical methods MNDO, PM3, and AM1 were also extended to third-row and fourthrow transition metals.…”

Section: Introductionmentioning

confidence: 99%

MSINDO parameterization for third‐row transition metals

2001

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ABSTRACT:The recently developed MSINDO version of the semiempirical SCF MO method SINDO1 has been parameterized for third-row transition metals Sc to Zn. The set of reference data used for the previous parameterization of SINDO1 has been substantially increased by incorporating results of recent experiments and first-principles calculations. A comparison of calculated heats of formation, geometries, ionization potentials, and dipole moments with literature values for more than 200 gas phase molecules is presented. The accuracy of the modified MSINDO version achieved for heats of formation and bond lengths has been considerably improved compared to SINDO1. Small clusters of transition metals and metal oxides were included in the parameterization to ensure accurate results for studies of larger systems. The application of the method to small transition metal complexes that were not included in the parameterization shows that the optimized parameters are transferable to other compounds.

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NDDO/MC: A new semiempirical SCFMO method for transition metal complexes

Cited by 38 publications

References 46 publications

Reduction of Nitroaromatic Compounds on the Surface of Metallic Iron: Quantum Chemical Study

Reduction of Nitroaromatic Compounds on the Surface of Metallic Iron: Quantum Chemical Study

Semiempirical molecular orbital models based on the neglect of diatomic differential overlap approximation

MSINDO parameterization for third‐row transition metals

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