The 6‐31G* and 6‐31G** basis sets previously introduced for first‐row atoms have been extended through the second‐row of the periodic table. Equilibrium geometries for one‐heavy‐atom hydrides calculated for the two‐basis sets and using Hartree–Fock wave functions are in good agreement both with each other and with the experimental data. HF/6‐31G* structures, obtained for two‐heavy‐atom hydrides and for a variety of hypervalent second‐row molecules, are also in excellent accord with experimental equilibrium geometries. No large deviations between calculated and experimental single bond lengths have been noted, in contrast to previous work on analogous first‐row compounds, where limiting Hartree–Fock distances were in error by up to a tenth of an angstrom. Equilibrium geometries calculated at the HF/6‐31G level are consistently in better agreement with the experimental data than are those previously obtained using the simple split‐valance 3‐21G basis set for both normal‐ and hypervalent compounds. Normal‐mode vibrational frequencies derived from 6‐31G* level calculations are consistently larger than the corresponding experimental values, typically by 10%–15%; they are of much more uniform quality than those obtained from the 3‐21G basis set. Hydrogenation energies calculated for normal‐ and hypervalent compounds are in moderate accord with experimental data, although in some instances large errors appear. Calculated energies relating to the stabilities of single and multiple bonds are in much better accord with the experimental energy differences.

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Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements

Gaussian-3 theory (G3 theory) for the calculation of molecular energies of compounds containing first (Li–F) and second row (Na–Cl) atoms is presented. This new theoretical procedure, which is based on ab initio molecular-orbital theory, modifies G2 theory [J. Chem. Phys. 94, 7221 (1991)] in several ways including a new sequence of single point energy calculations using different basis sets, a new formulation of the higher level correction, a spin–orbit correction for atoms, and a correction for core correlation. G3 theory is assessed using 299 energies from the G2/97 test set including enthalpies of formation, ionization potentials, electron affinities, and proton affinities. This new procedure corrects many of the deficiencies of G2 theory. There is a large improvement for nonhydrogen systems such as SiF4 and CF4, substituted hydrocarbons, and unsaturated cyclic species. Core-related correlation is found to be a significant factor, especially for species with unsaturated rings. The average absolute devi...

Gaussian-3 (G3) theory for molecules containing first and second-row atoms

We apply the long-range correction (LC) scheme for exchange functionals of density functional theory to time-dependent density functional theory (TDDFT) and examine its efficiency in dealing with the serious problems of TDDFT, i.e., the underestimations of Rydberg excitation energies, oscillator strengths, and charge-transfer excitation energies. By calculating vertical excitation energies of typical molecules, it was found that LC-TDDFT gives accurate excitation energies, within an error of 0.5 eV, and reasonable oscillator strengths, while TDDFT employing a pure functional provides 1.5 eV lower excitation energies and two orders of magnitude lower oscillator strengths for the Rydberg excitations. It was also found that LC-TDDFT clearly reproduces the correct asymptotic behavior of the charge-transfer excitation energy of ethylene-tetrafluoroethylene dimer for the long intramolecular distance, unlike a conventional far-nucleus asymptotic correction scheme. It is, therefore, presumed that poor TDDFT results for pure functionals may be due to their lack of a long-range orbital-orbital interaction.

A long-range-corrected time-dependent density functional theory

Jaguar is an ab initio quantum chemical program that specializes in fast electronic structure predictions for molecular systems of medium and large size. Jaguar focuses on computational methods with reasonable computational scaling with the size of the system, such as density functional theory (DFT) and local second-order Moller–Plesset perturbation theory. The favorable scaling of the methods and the high efficiency of the program make it possible to conduct routine computations involving several thousand molecular orbitals. This performance is achieved through a utilization of the pseudospectral approximation and several levels of parallelization. The speed advantages are beneficial for applying Jaguar in biomolecular computational modeling. Additionally, owing to its superior wave function guess for transition-metal-containing systems, Jaguar finds applications in inorganic and bioinorganic chemistry. The emphasis on larger systems and transition metal elements paves the way toward developing Jaguar for its use in materials science modeling. The article describes the historical and new features of Jaguar, such as improved parallelization of many modules, innovations in ab initio pKa prediction, and new semiempirical corrections for nondynamic correlation errors in DFT. Jaguar applications in drug discovery, materials science, force field parameterization, and other areas of computational research are reviewed. Timing benchmarks and other results obtained from the most recent Jaguar code are provided. The article concludes with a discussion of challenges and directions for future development of the program. © 2013 Wiley Periodicals, Inc.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/qua.24481

Jaguar: A high-performance quantum chemistry software program with strengths in life and materials sciences

Ab Initio Methods for the Calculation of NMR Shielding and Indirect Spin-Spin Coupling Constants

Contracted Gaussian basis sets for molecular calculations are derived from uncontracted (12,8) and (12,9) sets for the neutral second row atoms, Z=11–18, and for the negative ions P−, S−, and Cl−. Calculations on Na...2p63p, 2P and Mg...2p63s3p, 3P are used to derive contracted Gaussian functions to describe the 3p orbital in these atoms, necessary in molecular applications. The derived basis sets range from minimal, through double‐zeta, to the largest set which has a triple‐zeta basis for the 3p orbital, double‐zeta for the remaining. Where necessary to avoid unacceptable energy losses in atomic wave functions expanded in the contracted Gaussians, a given uncontracted Gaussian function is used in two contracted functions. These tabulations provide a hierarchy of basis sets to be used in designing a convergent sequence of molecular computations, and to establish the reliability of the molecular properties under study.

A. D. McLean

Papers

Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18