Optimization of parameters for semiempirical methods V: Modification of NDDO approximations and application to 70 elements

AbstractSeveral modifications that have been made to the NDDO core-core interaction term and to the method of parameter optimization are described. These changes have resulted in a more complete parameter optimization, called PM6, which has, in turn, allowed 70 elements to be parameterized. The average unsigned error (AUE) between calculated and reference heats of formation for 4,492 species was 8.0 kcal mol−1. For the subset of 1,373 compounds involving only the elements H, C, N, O, F, P, S, Cl, and Br, the PM6 AUE was 4.4 kcal mol−1. The equivalent AUE for other methods were: RM1: 5.0, B3LYP 6–31G*: 5.2, PM5: 5.7, PM3: 6.3, HF 6–31G*: 7.4, and AM1: 10.0 kcal mol−1. Several long-standing faults in AM1 and PM3 have been corrected and significant improvements have been made in the prediction of geometries. FigureCalculated structure of the complex ion [Ta6Cl12]2+ (footnote): Reference value in parenthesis

[1]  J. Pople,et al.  Approximate Self-Consistent Molecular Orbital Theory. I. Invariant Procedures , 1965 .

[2]  J. Bearden,et al.  Atomic energy levels , 1965 .

[3]  J. Pople,et al.  Approximate Self‐Consistent Molecular‐Orbital Theory. V. Intermediate Neglect of Differential Overlap , 1967 .

[4]  Michael J. S. Dewar,et al.  Ground states of molecules. XXV. MINDO/3. Improved version of the MINDO semiempirical SCF-MO method , 1975 .

[5]  M. Dewar,et al.  Ground States of Molecules. 38. The MNDO Method. Approximations and Parameters , 1977 .

[6]  Walter Thiel,et al.  Ground States of Molecules. 39. MNDO Results for Molecules Containing Hydrogen, Carbon, Nitrogen, and Oxygen , 1977 .

[7]  P. Pulay.  Convergence acceleration of iterative sequences. the case of scf iteration , 1980 .

[8]  Eamonn F. Healy,et al.  Development and use of quantum mechanical molecular models. 76. AM1: a new general purpose quantum mechanical molecular model , 1985 .

[9]  J. Schwartz,et al.  Organometallics , 1987, Science.

[10]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[11]  M. Dewar,et al.  AM1 calculations for compounds containing boron , 1988 .

[12]  J. Stewart.  Optimization of parameters for semiempirical methods II. Applications , 1989 .

[13]  J. Stewart.  Optimization of parameters for semiempirical methods I. Method , 1989 .

[14]  J. Stewart.  Optimization of parameters for semiempirical methods. III Extension of PM3 to Be, Mg, Zn, Ga, Ge, As, Se, Cd, In, Sn, Sb, Te, Hg, Tl, Pb, and Bi , 1991 .

[15]  W. Thiel,et al.  Extension of the MNDO formalism tod orbitals: Integral approximations and preliminary numerical results , 1992 .

[16]  Jackson,et al.  Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. , 1992, Physical review. B, Condensed matter.

[17]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[18]  Ernst Anders,et al.  Optimization and application of lithium parameters for PM3 , 1993, J. Comput. Chem..

[19]  George P. Ford,et al.  Atomic charges derived from a fast and accurate method for electrostatic potentials based on modified AM1 calculations , 1994, J. Comput. Chem..

[20]  Walter Thiel,et al.  Extension of MNDO to d Orbitals: Parameters and Results for the Second-Row Elements and for the Zinc Group , 1996 .

[21]  Notker Rösch,et al.  AM1/d Parameters for Molybdenum , 2000 .

[22]  Matthew L. Leininger,et al.  Anchoring the water dimer potential energy surface with explicitly correlated computations and focal point analyses , 2002 .

[23]  F. Allen.  The Cambridge Structural Database: a quarter of a million crystal structures and rising. , 2002, Acta crystallographica. Section B, Structural science.

[24]  James J P Stewart,et al.  Optimization of parameters for semiempirical methods IV: extension of MNDO, AM1, and PM3 to more main group elements , 2004, Journal of molecular modeling.

[25]  J. Stewart.  Use of Semiempirical Methods for Detecting Anomalies in Reported Enthalpies of Formation of Organic Compounds , 2004 .

[26]  James J. P. Stewart,et al.  Comparison of the accuracy of semiempirical and some DFT methods for predicting heats of formation , 2004, Journal of molecular modeling.

[27]  Darrin M York,et al.  A Semiempirical Quantum Model for Hydrogen-Bonded Nucleic Acid Base Pairs. , 2005, Journal of chemical theory and computation.

[28]  Timothy Clark,et al.  AM1* parameters for aluminum, silicon, titanium and zirconium , 2005, Journal of molecular modeling.

[29]  Jun Ge,et al.  Can the semiempirical PM3 scheme describe iron‐containing bioinorganic molecules? , 2006, J. Comput. Chem..

[30]  G. M. Arantes,et al.  Specific parametrisation of a hybrid potential to simulate reactions in phosphatases. , 2006, Physical chemistry chemical physics : PCCP.

[31]  Alfredo Mayall Simas,et al.  RM1: A reparameterization of AM1 for H, C, N, O, P, S, F, Cl, Br, and I , 2006, J. Comput. Chem..

[32]  Àngels González-Lafont,et al.  A PM3/d specific reaction parameterization for iron atom in the hydrogen abstraction catalyzed by soybean lipoxygenase‐1 , 2007, J. Comput. Chem..