On some ways of modifying semiempirical quantum chemical methods

Zhidomirov, G. M.; Zhanpeisov, Nurbosyn U.; Zilberberg, Igor L.; Yudanov, Ilya V.

doi:10.1002/(sici)1097-461x(1996)58:2<175::aid-qua6>3.0.co;2-v

Cited by 7 publications

(3 citation statements)

References 48 publications

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“…An exact orthogonalization of χ H (eg, by the transformation

^{χ} S^{- \frac{1}{2} χ} H^{χ} S^{- \frac{1}{2}}

) was initially attempted, but did not provide a useful model to calculate electronic energies as confirmed by other studies . Kolb and Thiel therefore decided to develop approximate orthogonalization corrections to be added to χ H .…”

Section: The Orthogonalization‐corrected Modelsmentioning

confidence: 99%

“…An exact orthogonalization of χ H (e.g., by the transformation χ S − 1 2 χ H χ S − 1 2 ) was initially attempted, but did not provide a useful model to claculate electroni energies 58,59,182 as confirmed by other studies. 122,154,159,[184][185][186][187] Kolb and Thiel therefore decided to develop approximate orthogonalization corrections to be added to χ H. 58,182 These 58, 59, 151, 182 and other 162,[188][189][190] approximate orthogonalization corrections, are based on an expansion of χ S − 1 2 into a power series,…”

Section: Approximation Of the Symmetrically Orthogonalized One-electr...mentioning

confidence: 99%

“…For other NDDO-SEMO models see also Refs. 104,[146][147][148]185,[193][194][195][196][197][198] 6.1 The Nonorthogonalized Modified Neglect of Differential Overlap (NO-MNDO) Model…”

Section: Other Nddo-semo Modelsmentioning

confidence: 99%

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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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“…An exact orthogonalization of χ H (eg, by the transformation

^{χ} S^{- \frac{1}{2} χ} H^{χ} S^{- \frac{1}{2}}

Section: The Orthogonalization‐corrected Modelsmentioning

confidence: 99%

Section: Approximation Of the Symmetrically Orthogonalized One-electr...mentioning

confidence: 99%

See 1 more Smart Citation

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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Theoretische Chemie 1996

Kaupp

Jug

Häser

1997

Nachr. Chem. Tech. Lab.

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Die Anwendung von Dichtefunktional‐und ab initio‐Methoden auf molekulare Übergangsmetallsysteme, die semiempirische Theorie größerer Systeme, wie Biomoleküle, Cluster und Festkörper, sowie das Potential theoretischer Methoden für die Chemie der Hauptgruppen, die Interpretation von NMR‐Spektren und das Verständnis bestimmter chemischer Phänomene sind diesmal Schwerpunkte des Trendberichts.

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Towards Fast and Reliable Quantum Chemical Modelling of Macromolecules

Laaksonen

New Algorithms for Macromolecular Simulation

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On some ways of modifying semiempirical quantum chemical methods

Cited by 7 publications

References 48 publications

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

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

Theoretische Chemie 1996

Towards Fast and Reliable Quantum Chemical Modelling of Macromolecules

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