Gaussian-4 theory using reduced order perturbation theory.

Two modifications of Gaussian-4 (G4) theory [L. A. Curtiss et al., J. Chem. Phys. 126, 084108 (2007)] are presented in which second- and third-order perturbation theories are used in place of fourth-order perturbation theory. These two new methods are referred to as G4(MP2) and G4(MP3), respectively. Both methods have been assessed on the G3/05 test set of accurate experimental data. The average absolute deviation from experiment for the 454 energies in this test set is 1.04 kcalmol for G4(MP2) theory and 1.03 kcalmol for G4(MP3) theory compared to 0.83 kcalmol for G4 theory. G4(MP2) is slightly more accurate for enthalpies of formation than G4(MP3) (0.99 versus 1.04 kcalmol), while G4(MP3) is more accurate for ionization potentials and electron affinities. Overall, the G4(MP2) method provides an accurate and economical method for thermochemical predictions. It has an overall accuracy for the G3/05 test set that is much better than G3(MP2) theory (1.04 versus 1.39 kcalmol) and even better than G3 theory (1.04 versus 1.13 kcalmol). In addition, G4(MP2) does better for challenging hypervalent systems such as H(2)SO(4) and for nonhydrogen species than G3(MP2) theory.

[1]  L. Curtiss,et al.  Gaussian‐1 theory: A general procedure for prediction of molecular energies , 1989 .

[2]  T. H. Dunning.  Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen , 1989 .

[3]  Krishnan Raghavachari,et al.  Gaussian‐1 theory of molecular energies for second‐row compounds , 1990 .

[4]  Krishnan Raghavachari,et al.  Gaussian-2 theory for molecular energies of first- and second-row compounds , 1991 .

[5]  Krishnan Raghavachari,et al.  Gaussian-2 theory using reduced Moller--Plesset orders , 1993 .

[6]  David Feller,et al.  The use of systematic sequences of wave functions for estimating the complete basis set, full configuration interaction limit in water , 1993 .

[7]  Angela K. Wilson,et al.  Gaussian basis sets for use in correlated molecular calculations. IX. The atoms gallium through krypton , 1993 .

[8]  Leo Radom,et al.  Gaussian‐2 (G2) theory: Reduced basis set requirements , 1996 .

[9]  L. Curtiss,et al.  Assessment of Gaussian-2 and density functional theories for the computation of enthalpies of formation , 1997 .

[10]  L. Curtiss,et al.  INVESTIGATION OF THE USE OF B3LYP ZERO-POINT ENERGIES AND GEOMETRIES IN THE CALCULATION OF ENTHALPIES OF FORMATION , 1997 .

[11]  Jan M. L. Martin.  Basis set convergence study of the atomization energy, geometry, and anharmonic force field of SO2: The importance of inner polarization functions , 1998 .

[12]  L. Curtiss,et al.  Gaussian-3 (G3) theory for molecules containing first and second-row atoms , 1998 .

[13]  Krishnan Raghavachari,et al.  Assessment of Gaussian-2 and density functional theories for the computation of ionization potentials and electron affinities , 1998 .

[14]  C. Bauschlicher,et al.  Atomization Energies of SO and SO2; Basis Set Extrapolation Revisted , 1998 .

[15]  Heat of atomization of sulfur trioxide, SO3: a benchmark for computational thermochemistry , 1999, physics/9907007.

[16]  Krishnan Raghavachari,et al.  Gaussian-3 theory using reduced Mo/ller-Plesset order , 1999 .

[17]  G. A. Petersson,et al.  A complete basis set model chemistry. VI. Use of density functional geometries and frequencies , 1999 .

[18]  Trygve Helgaker,et al.  Basis-set convergence of the energy in molecular Hartree–Fock calculations , 1999 .

[19]  Jan M. L. Martin,et al.  TOWARDS STANDARD METHODS FOR BENCHMARK QUALITY AB INITIO THERMOCHEMISTRY :W1 AND W2 THEORY , 1999, physics/9904038.

[20]  L. Curtiss,et al.  Gaussian-3 theory: a variation based on third-order perturbation theory and an assessment of the contribution of core-related correlation , 1999 .

[21]  K. Peterson,et al.  Re-examination of atomization energies for the Gaussian-2 set of molecules , 1999 .

[22]  D. Truhlar,et al.  Multi-coefficient Gaussian-3 method for calculating potential energy surfaces , 1999 .

[23]  Krishnan Raghavachari,et al.  GAUSSIAN-3 THEORY USING DENSITY FUNCTIONAL GEOMETRIES AND ZERO-POINT ENERGIES , 1999 .

[24]  D. Truhlar,et al.  MULTI-COEFFICIENT CORRELATION METHOD FOR QUANTUM CHEMISTRY , 1999 .

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

[26]  John A. Montgomery,et al.  A complete basis set model chemistry. VII. Use of the minimum population localization method , 2000 .

[27]  Krishnan Raghavachari,et al.  Assessment of Gaussian-3 and Density Functional Theories for Enthalpies of Formation of C1−C16 Alkanes† , 2000 .

[28]  L. Curtiss,et al.  Assessment of Gaussian-3 and density functional theories for a larger experimental test set , 2000 .

[29]  Angela K. Wilson,et al.  Gaussian basis sets for use in correlated molecular calculations. X. The atoms aluminum through argon revisited , 2001 .

[30]  L. Curtiss,et al.  Gaussian-3X (G3X) theory : use of improved geometries, zero-point energies, and Hartree-Fock basis sets. , 2001 .

[31]  L. Curtiss,et al.  The definition of core electrons. , 2001 .

[32]  D. Dixon,et al.  Extended benchmark studies of coupled cluster theory through triple excitations , 2001 .

[33]  Donald G. Truhlar,et al.  Robust and Affordable Multicoefficient Methods for Thermochemistry and Thermochemical Kinetics: The MCCM/3 Suite and SAC/3 , 2003 .

[34]  T. Dunning,et al.  SO2 revisited: Impact of tight d augmented correlation consistent basis sets on structure and energetics , 2003 .

[35]  Mihaly Kallay,et al.  W3 theory: robust computational thermochemistry in the kJ/mol accuracy range. , 2003, Journal of Chemical Physics.

[36]  Juana Vázquez,et al.  HEAT: High accuracy extrapolated ab initio thermochemistry. , 2004, The Journal of chemical physics.

[37]  T. Dunning,et al.  The HSO−SOH Isomers Revisited: The Effect of Tight d Functions† , 2004 .

[38]  L. Curtiss,et al.  Assessment of Gaussian-3 and density-functional theories on the G3/05 test set of experimental energies. , 2005, The Journal of chemical physics.

[39]  Geoffrey P. F. Wood,et al.  A restricted-open-shell complete-basis-set model chemistry. , 2006, The Journal of chemical physics.

[40]  Heats of formation of perchloric acid, HClO4, and perchloric anhydride, Cl2O7. Probing the limits of W1 and W2 theory , 2005, physics/0508076.

[41]  Nathan J DeYonker,et al.  The correlation-consistent composite approach: application to the G3/99 test set. , 2006, The Journal of chemical physics.

[42]  D. Dixon,et al.  Ab initio prediction of the gas- and solution-phase acidities of strong Brønsted acids: the calculation of pKa values less than -10. , 2006, The journal of physical chemistry. A.

[43]  B. Ruscic,et al.  W4 theory for computational thermochemistry: In pursuit of confident sub-kJ/mol predictions. , 2006, The Journal of chemical physics.

[44]  Kalju Kahn,et al.  Convergence of third order correlation energy in atoms and molecules , 2007, J. Comput. Chem..

[45]  L. Curtiss,et al.  Gaussian-4 theory. , 2007, The Journal of chemical physics.