A new approach to counterpoise correction to BSSE

In the present work the intermolecular BSSE, associated to the A–B interaction, is obtained by subtracting the intramolecular BSSE of the fragments from the intramolecular BSSE of the supermolecule, and considering every atom as a fragment in the calculation of each intramolecular BSSE. This atom by atom scheme (CPaa) is based on the consideration that the proximity of the fragments may affect the intramolecular BSSE of every involved species, and artificially influences the value of the BSSE associated to the supermolecule formation. It drastically decreases the reported counterpoise overcorrection of the A–B interaction, even though it does not deal with all the overcorrection because it includes all the orbitals, and not only the unoccupied ones. This new approach has been tested on the water dimer, some hydrogen fluoride weakly bonded complexes, the conformational analysis of 1,2‐dichloroethane, and the reaction profile of formaldehyde + OH reaction. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 1203–1210, 2006

[1]  H. B. Jansen,et al.  Non-empirical molecular orbital calculations on the protonation of carbon monoxide , 1969 .

[2]  F. B. van Duijneveldt,et al.  Weakly Bonded Systems , 2007 .

[3]  P. Surján,et al.  Improved intermolecular SCF theory and the BSSE problem , 1989 .

[4]  István Mayer,et al.  Hierarchy of counterpoise corrections for N-body clusters: generalization of the Boys-Bernardi scheme , 1997 .

[5]  M. Mella,et al.  Three-Fragment Counterpoise Correction of Potential Energy Curves for Proton-Transfer Reactions , 2003 .

[6]  T. Dunning,et al.  A Road Map for the Calculation of Molecular Binding Energies , 2000 .

[7]  K. Leopold,et al.  Molecular and Electronic Structure of C5H5N−SO3: Correlation of Ground State Physical Properties with Orbital Energy Gaps in Partially Bound Lewis Acid−Base Complexes , 2001 .

[8]  Trygve Helgaker,et al.  Highly accurate calculations of molecular electronic structure , 1999 .

[9]  A. D. McLean,et al.  Accurate calculation of the attractive interaction of two ground state helium atoms , 1973 .

[10]  Peter Pulay,et al.  The local correlation treatment. II. Implementation and tests , 1988 .

[11]  H. Valdés,et al.  Ab initio and DFT studies on van der Waals trimers: The OCS · (CO2)2 complexes , 2002, J. Comput. Chem..

[12]  Peter R. Taylor,et al.  General contraction of Gaussian basis sets. I. Atomic natural orbitals for first‐ and second‐row atoms , 1987 .

[13]  P. Salvador,et al.  Counterpoise Corrected Ion/Molecule Complexes Using Two or Three Fragments , 2002 .

[14]  A. Meunier,et al.  Corrélation électronique et effets de base dans l'étude de la liaison hydrogène: le dimère mixte ammoniac-eau , 1973 .

[15]  Larry A. Curtiss,et al.  Studies of molecular association in H2O and D2O vapors by measurement of thermal conductivity , 1979 .

[16]  M. Szczęśniak,et al.  Origins of Structure and Energetics of van der Waals Clusters from ab Initio Calculations , 1994 .

[17]  J. J. Dannenberg,et al.  Molecular orbital calculations of water clusters on counterpoise-corrected potential energy surfaces , 2004 .

[18]  N. Kestner.  He–He Interaction in the SCF–MO Approximation , 1968 .

[19]  H. Valdés,et al.  Ab Initio Study on the (OCS)2·CO2 van der Waals Trimers , 2002 .

[20]  A. J. Sadlej.  Exact perturbation treatment of the basis set superposition correction , 1991 .

[21]  N. Kestner,et al.  Basis Set Superposition Errors: Theory and Practice , 2007 .

[22]  J. Dannenberg,et al.  Correcting for basis set superposition error in aggregates containing more than two molecules: Ambiguities in the calculation of the counterpoise correction , 1993 .

[23]  Stephen Wilson,et al.  Intramolecular basis set superposition errors , 2001 .

[24]  S. F. Boys,et al.  The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors , 1970 .

[25]  Michael L. Klein,et al.  Intermolecular potential functions and the properties of water , 1982 .

[26]  J. Dannenberg,et al.  Effect of Basis Set Superposition Error (BSSE) upon ab Initio Calculations of Organic Transition States , 2001 .

[27]  J. López,et al.  The tetrahydrofuran⋯hydrogen chloride complex: Rotational spectrum and theoretical analysis , 1999 .

[28]  P. Claverie,et al.  Perturbative ab initio calculations of intermolecular energies. I. Method , 1974 .

[29]  István Mayer,et al.  Second order Mo/ller–Plesset perturbation theory without basis set superposition error , 1998 .

[30]  H. Schaefer,et al.  Extensive theoretical studies of the hydrogen‐bonded complexes (H2O)2, (H2O)2H+, (HF)2, (HF)2H+, F2H−, and (NH3)2 , 1986 .

[31]  M. Sironi,et al.  New basis set superposition error free ab initio MO-VB interaction potential: Molecular-dynamics simulation of water at critical and supercritical conditions , 1998 .

[32]  F. Jensen.  THE MAGNITUDE OF INTRAMOLECULAR BASIS SET SUPERPOSITION ERROR , 1996 .

[33]  E. Davidson,et al.  An analysis of the hydrogen bond in ice , 1990 .

[34]  J. V. Lenthe,et al.  State of the Art in Counterpoise Theory , 1994 .

[35]  Donald G. Truhlar,et al.  Systematic study of basis set superposition errors in the calculated interaction energy of two HF molecules , 1985 .

[36]  P. Kollman,et al.  An application of the functional Boys-Bernardi counterpoise method to molecular potential surfaces , 1973 .