Approximate Atomic Wavefunctions

Huzinaga, Sigeru; McWilliams, D.; Domsky, B.

doi:10.1063/1.1675170

Cited by 280 publications

(170 citation statements)

References 4 publications

Supporting

Mentioning

166

Contrasting

Unclassified

Order By: Relevance

“…The ab irzitio reference calculations were carried out with double-2; quality basis sets for S, Se, and Te, respectively (28) …”

Section: Methods and Computational Detailsmentioning

confidence: 99%

Structure and bonding in square-planar chalcogen rings

Sæthre¹,

Gropen²

1992

Can. J. Chem.

View full text Add to dashboard Cite

This paper is dedicaterl to Profe>.s.sor Sigerx Hlrzirltrgcr or1 tile oc.ctl.c.ior~ of'11i.s 65th Oirtl~rltr~ LEIF J. SAETHRE and ODD GROI>EN. Can. J . Chern. 70, 348 ( 1992).The molecular structures of square-planar x,"., X,', and X, (X = S , Se, Te) have been calculated using the effective core potential model. For x," the agreement between experimental and calculated valucs is excellent provided that d orbitals are included in the basis set. For the hypothetical niolecules X,' and X, the bond lengths are found to increase dramatically as one and, subsequently, two electrons are added to the systems. Extensive population analysis shows that this increase is almost exclusively due to loss of bonding in the .rr system, whereas the bonding in the a system remains relatively unaltered. These results make it possible to predict covalent single bond radii for S , Se, and Te for which the influence of .rr repulsion is removed. From the calculated variation of bond lengths with atomic charge, bond lengths are predicted for a series of planar disulphide rings.

show abstract

“…The ab irzitio reference calculations were carried out with double-2; quality basis sets for S, Se, and Te, respectively (28) …”

Section: Methods and Computational Detailsmentioning

confidence: 99%

Structure and bonding in square-planar chalcogen rings

Sæthre¹,

Gropen²

1992

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…Based on a recent implementation of indirect spinspin coupling constants at the DFT level [16], we have included the solvent contributions using the PCM model to the singlet and linear response functions as described in Section 2. A study by Helgaker et al [5] demonstrated that basis sets based on Huzinaga's compilation [37] with polarization functions by van Wüllen [38], decontracted in the s space and with additional tight s functions, provide a good compromise between the accuracy of the results and the size of the basis set. We will in this work employ the Huz-IIsu2 basis set [5] where two tight s functions have been added to the atomic Huz-II basis set in a geometric progression.…”

Section: Computational Detailsmentioning

confidence: 99%

Solvent Effects on the Indirect Spin–Spin Coupling Constants of Benzene: The DFT-PCM Approach

Ruud

Frediani

Cammi

et al. 2003

IJMS

View full text Add to dashboard Cite

Abstract:We present an extension of the Polarizable Continuum Model (PCM) to the calculation of solvent effects on indirect spin-spin coupling constants for HartreeFock wave functions and Density Functional Theory. This is achieved by implementing the PCM model for singlet and triplet linear response functions. The new code is used for calculating the solvent effects on the indirect spin-spin coupling constants of benzene. For the 1 J(H 13 C) coupling constants, our calculated solvent shifts are in good agreement with experimental observations when geometry relaxation is taken into account. However, our results do not support the extrapolated gas-phase value for this coupling constant. A new experimentally derived 1 J(H 13 C) for a vibrating benzene molecule at 300 K is proposed.

show abstract

“…In the contracted basis the 4d orbitals are represented by a triple zeta function while all other orbitals including the unoccupied 5 p orbitals are represented by double zeta functions. For the C atom we have used Huzinaga's (10s,6p) basis, 14 but it has been augmented by a d polarization function with exponent 0.75. The basis set for the C atom has been contracted to (4s,3p,1d) resulting in double zeta representation of the s functions, triple zeta representation of the 2 p function, and a d polarization function.…”

Section: Basis Sets and Hf Calculations On Mocmentioning

confidence: 99%

Electronic states and nature of bonding in the molecule MoC by all electron ab initio calculations

Shim

Gingerich

1997

The Journal of Chemical Physics

View full text Add to dashboard Cite

In the present work all electron ab initio multiconfiguration self-consistent-field (CASSCF) and multireference configuration interaction (MRCI) calculations have been carried out to determine the low-lying electronic states of the molecule MoC. The relativistic corrections for the one electron Darwin contact term and the relativistic mass-velocity correction have been determined in perturbation calculations. The electronic ground state is predicted as Σ3−. The spectroscopic constants for the Σ3− electronic ground state and eight low-lying excited states have been derived by solving the Schrödinger equation for the nuclear motion numerically. Based on the results of the CASSCF calculations the Σ3− ground state of MoC is separated from the excited states Δ3,Σ5−,Γ3,Δ1,Π5,Σ1+ and Π3 by transition energies of 4500, 6178, 7207, 9312, 10 228, 11 639, and 16 864 cm−1, respectively. The transition energy between the Σ3− ground state and the Π3 state as derived in the MRCI calculations is 15 484 cm−1. For the Σ3− ground state the equilibrium distance has been determined as 1.688 Å, and the vibrational frequency as 997 cm−1. The chemical bond in the Σ3− electronic ground state has triple bond character due to the formation of delocalized bonding π and σ orbitals. The chemical bond in the MoC molecule is polar with charge transfer from Mo to C, giving rise to a dipole moment of 6.15 D at 3.15 a.u. in the Σ3− ground state.

show abstract

Approximate Atomic Wavefunctions

Cited by 280 publications

References 4 publications

Structure and bonding in square-planar chalcogen rings

Structure and bonding in square-planar chalcogen rings

Solvent Effects on the Indirect Spin–Spin Coupling Constants of Benzene: The DFT-PCM Approach

Electronic states and nature of bonding in the molecule MoC by all electron ab initio calculations

Contact Info

Product

Resources

About