A systematic determination of extended atomic orbital basis sets and application to molecular SCF and MCSCF calculations (original) (raw)
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Basis set selection for molecular calculations
Chemical Reviews, 1986
00082665/8610788-0881$~.50/0 I . Ernest R. Davfdson was born in Terre Haute. IN. in 1938. He reghnrd a B.Sc. w e e in chermcal engindng from RoseHman InsUtute in 1958 and his Ph.D. in 1961 from Indiana University In chemistry. He was an NSF postdoctoral fellow at the University of Wismnsh in 1961. From 1962 until 1984 he was on the facuity at the university of Washington. I n 1984 he returned to Indiana University where he is presently a distinguished professor and director of the Guantum Chemlshy Program Exchange and of the Chemical Physics program. He was elected to the International Academy of Molecular Quantum Science in 1981. He has over 200 publications in the field of computational quantum chemistry including work on denslty matrices, charge. spin. and momentum distributions. electronic Structure of excited states. the Structure of organic radicals and diradicals, and ab initio computational methods. Daw FwM was ban h Dlhqtie, IA, in 1950. He rwceivwd a B.S. w e e from Loras COILS@ in 1972 and a PhD. in physical chem lsby from Iowa State University under the direction of Professor Kbus Ruedenberg In 1979. He then ioined the research groups 01 Professors Wes W d e n and Ernest Davidson at the University of Washington as a postdoctoral associate. I n 1982 he was p a m t e d to Um poWm of Research AssocktelFanmy. Cunently he holds an Associate Scientist posmn at Indiana University. His research interests include the application of very extended basis set ab initio techniques for determining molecular properties.
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
The Journal of Chemical Physics, 1992
The calculation of accurate electron affinities (EAs) of atomic or molecular species is one of the most challenging tasks in quantum chemistry. We describe a reliable procedure for calculating the electron affinity of an atom and present results for hydrogen, boron, carbon, oxygen, and fluorine (hydrogen is included for completeness). This procedure involves the use of the recently proposed correlation-consistent basis sets augmented with functions to describe the more diffuse character of the atomic anion coupled with a straightforward, uniform expansion of the reference space for multireference singles and doubles configurationinteraction (MRSD-Cl) calculations. Comparison with previous results and with corresponding full CI calculations are given. The most accurate EAs obtained from the MRSD-CI calculations are (with experimental values in parentheses) hydrogen 0.740 eV (0.754), boron 0.258 (0.277), carbon 1.245 (1.263), oxygen 1.384 (1.461), and fluorine 3.337 (3.40 1). The EAs obtained from the MR-SDCI calculations differ by less than 0.03 e V from those predicted by the full CI calculations.
Wiley Interdisciplinary Reviews: Computational Molecular Science, 2012
Electronic structure methods for molecular systems rely heavily on using basis sets composed of Gaussian functions for representing the molecular orbitals. A number of hierarchical basis sets have been proposed over the last two decades, and they have enabled systematic approaches to assessing and controlling the errors due to incomplete basis sets. We outline some of the principles for constructing basis sets, and compare the compositions of eight families of basis sets that are available in several different qualities and for a reasonable number of elements in the periodic table.
The electron cusp condition and the virial ratio as indicators of basis set quality
The Journal of Chemical Physics, 2003
We consider two measures of the quality of one-electron basis sets for quantum-chemical calculations: The electron-electron coalescence curvature and the correlation energy virial ratio. The former is based on the Kato cusp condition that many-electron wave functions must exhibit discontinuous first derivatives with respect to r 12 as the coordinates of any two electrons coalesce. The latter is based on a simple modification of the quantum-mechanical virial theorem that makes use of only the correlation contributions to the kinetic and potential energy expectation values. The two measures are tested using coupled cluster wave functions for helium, neon, argon, calcium, and phosphorus atoms and are found to indicate good correlation with the quality of the basis set. These techniques may provide a foundation for the development of reliable basis set diagnostics for a variety of quantum-chemical applications.
Method for atomic calculations
Physical review, 1989
Rapid Communications The Rapid Communications section is intended for the accelerated publication of important new results. Since manuscripts submitted to this section are gicen priority treatment both in the editorial once and in production, authors should explain in their submittal letter why the work j ustiftes this special handling A.Rapid Communication should be no longer than 3' printed pages and must be accompanied by an abstract.
Journal of Molecular Structure: THEOCHEM, 1997
Although Hartree-Fock wave functions can provide a semi-quantitative description of the electronic structure of molecules, accurate predictions cannot be made without explicit inclusion of the effects of electron correlation. In correlated calculations, the accuracy of the wave function is determined by two expansions: the many-electron expansion in terms of molecular orbitals that defines the form of the wave function and the basis set used to expand the one-electron molecular orbitals. Thus, to assess the accuracy of a given wave function (correlation method), it is necessary to examine the dependence of a given property on the basis set. In this work, systematic sequences of correlation consistent basis sets ranging in size from double-to sextuple-zeta (cc-pVnZ) have been employed together with several commonly used electron correlation methods, e.g., MPn (n = 2-4) CCSD, CCSD(T), and MRCI, to calculate the spectroscopic constants and selected molecular properties of the carbon monoxide molecule. The computed spectroscopic constants show excellent convergence toward the complete basis set (CBS) limit, and the inrrinsic errors of each correlation method have been assessed and compared. The effects of correlating the 1 s-like core electrons have also been determined using a sequence of core-valence cc-pCVnZ basis sets with the CCSD(T) and ACPF methods. A number of other properties have also been calculated for each correlation method as a function of the correlation consistent basis set: the dipole moment, quadrupole moment, dipole polarizability, and the first and second hyperpolarizabilities. For these calculations, results using the aug-cc-pVnZ basis sets are compared with those obtained using basis sets incorporating another complete shell of diffuse functions, d-aug-cc-pVnZ.
6‐31G* basis set for third‐row atoms
Journal of Computational Chemistry, 2001
are developed for the third-row elements Ga through Kr. The basis functions generalize the 6-31G and 6-31G * sets commonly used for atoms up to Ar. A reexamination of the 6-31G * basis set for K and Ca developed earlier leads to the inclusion of 3d orbitals into the valence space for these atoms. Now the 6-31G basis for the whole third-row K through Kr has six primitive Gaussians for 1s, 2s, 2p, 3s, and 3p orbitals, and a split-valence pair of three and one primitives for valence orbitals, which are 4s, 4p, and 3d. The nature of the polarization functions for third-row atoms is reexamined as well. The polarization functions for K, Ca, and Ga through Kr are single set of Cartesian d-type primitives. The polarization functions for transition metals are defined to be a single 7f set of uncontracted primitives. Comparison with experimental data shows good agreement with bond lengths and angles for representative vapor-phase metal complexes.