No abstract

The Gaussian-2 theoretical procedure (G2 theory), based on ab initio molecular orbital theory, for calculation of molecular energies (atomization energies, ionization potentials, electron affinities, and proton affinities) of compounds containing first- (Li–F) and second-row atoms (Na–Cl) is presented. This new theoretical procedure adds three features to G1 theory [J. Chem. Phys. 90, 5622 (1989)] including a correction for nonadditivity of diffuse-sp and 2df basis set extensions, a basis set extension containing a third d function on nonhydrogen and a second p function on hydrogen atoms, and a modification of the higher level correction. G2 theory is a significant improvement over G1 theory because it eliminates a number of deficiencies present in G1 theory. Of particular importance is the improvement in atomization energies of ionic molecules such as LiF and hydrides such as C2H6, NH3, N2H4, H2O2, and CH3SH. The average absolute deviation from experiment of atomization energies of 39 first-row compounds is reduced from 1.42 to 0.92 kcal/mol. In addition, G2 theory gives improved performance for hypervalent species and electron affinities of second-row species (the average deviation from experiment of electron affinities of second-row species is reduced from 1.94 to 1.08 kcal/mol). Finally, G2 atomization energies for another 43 molecules, not previously studied with G1 theory, many of which have uncertain experimental data, are presented and differences with experiment are assessed.

The direct (recomputation of two-electron integrals) implementation of the gauge-including atomic orbital (GIAO) and the CSGT (continuous set of gauge transformations) methods for calculating nuclear magnetic shielding tensors at both the Hartree-Fock and density functional levels of theory are presented. Isotropic 13C, 15N, and 17O magnetic shielding constants for several molecules, including taxol (C47H51NO14 using 1032 basis functions) are reported. Shielding tensor components determined using the GIAO and CSGT methods are found to converge to the same value at sufficiently large basis sets; however, GIAO shielding tensor components for atoms other than carbon are found to converge faster with respect to basis set size than those determined using the CSGT method for both Hartree-Fock and DFT. For molecules where electron correlation effects are significant, shielding constants determined using (gradient-corrected) pure DFT or hybrid methods (including a mixture of Hartree-Fock exchange and DFT exchange-correlation) are closer to experiment than those determined at the Hartree-Fock level of theory. For the series of molecules studied here, the RMS error for 13C chemical shifts relative to TMS determined using the B3LYP hybrid functional with the 6-311+G(2d,p) basis is nearly three times smaller than the RMS error for shifts determined using Hartree-Fock at this same basis. Hartree-Fock 13C chemical shifts calculated using the 6-31G* basis set give nearly the same RMS error as compared to experiment as chemical shifts obtained using Hartree-Fock with the bigger 6-311+G(2d,p) basis set for the range of molecules studied here. The RMS error for chemical shifts relative to TMS calculated at the Hartree-Fock 6-31G* level of theory for taxol (C47H51NO14) is 6.4 ppm, indicating that for large systems, this level of theory is sufficient to determine accurate 13C chemical shifts.

Aqueous HF etching of silicon surfaces results in the removal of the surface oxide and leaves behind silicon surfaces terminated by atomic hydrogen. The effect of varying the solution pH on the surface structure is studied by measuring the SiH stretch vibrations with infrared absorption spectroscopy. Basic solutions ( pH=9–10) produce ideally terminated Si(111) surfaces with silicon monohydride ( 3/4 SiH) oriented normal to the surface. The surface is found to be very homogeneous with low defect density (<0.5%) and narrow vibrational linewidth (0.95 cm−1 ).

The low-lying dns2→dn+1s1 excitation energies of the first row transition metal atoms Sc–Cu are calculated using fourth-order M≂ller–Plesset perturbation theory (MP4) as well as quadratic configuration interaction (QCI) techniques with large spd and spdf  basis sets. The MP4 method performs well for Sc–Mn but fails dramatically for Fe–Cu. In contrast, the QCI technique performs uniformly for all excitation energies with a mean deviation from experiment of only 0.14 eV after including relativistic corrections. f functions contribute 0.1–0.4 eV to the excitation energies for these systems. The highly correlated d10 state of the Ni atom is also considered in detail. The QCI technique obtains the d9s1→d10 splitting of the Ni atom with an error of only 0.13 eV. The results show that single-configuration Hartree–Fock based methods can be successful in calculating excitation energies of transition metal atoms.