Adiabatic Polarization Potentials for the Water and Nitrogen Molecules. A Comparison of Large and Small Basis Sets

DouglassJr., C. H.; Weil, David A.; Charlier, Patricia A.; Eades, Robert A.; Truhlar, Donald G.; Dixon, David A.

doi:10.1007/978-1-4757-9634-6_9

Cited by 10 publications

(3 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Accurate calculations of electrical properties of molecules often require large basis sets, including multiple polarization functions and diffuse functions. − It is therefore interesting to study the need for higher-angular-momentum diffuse functions, and we present some calculations exploring this need in this section.…”

Section: Wave Function Calculations Of Van Der Waals Potential Curves...mentioning

confidence: 99%

Perspectives on Basis Sets Beautiful: Seasonal Plantings of Diffuse Basis Functions

Papajak

Zheng

et al. 2011

J. Chem. Theory Comput.

Self Cite

665

593

View full text Add to dashboard Cite

We present a perspective on the use of diffuse basis functions for electronic structure calculations by density functional theory and wave function theory. We especially emphasize minimally augmented basis sets and calendar basis sets. We base our conclusions on our previous experience with commonly computed quantities, such as bond energies, barrier heights, electron affinities, noncovalent (van der Waals and hydrogen bond) interaction energies, and ionization potentials, on Stephens et al.'s results for optical rotation and on our own new calculations (presented here) of polarizabilities and of potential energy curves of van der Waals complexes. We emphasize the benefits of partial augmentation of the higher-zeta basis sets in preference to full augmentation at a lower ζ level. Benefits and limitations of the use of fully, partially, and minimally augmented basis sets are reviewed for different electronic structure methods and molecular properties. We have found that minimal augmentation is almost always enough for density functional theory (DFT) when applied to ionization potentials, electron affinities, atomization energies, barrier heights, and hydrogen-bond energies. For electric dipole polarizabilities, we find that augmentation beyond minimal has an average effect of 8% at the polarized triple-ζ level and 5% at the polarized quadruple-ζ level. The effects are larger for potential energy curves of van der Waals complexes. The effects are also larger for wave function theory (WFT). Even for WFT though, full augmentation is not needed for most purposes, and a level of augmentation between minimal and full is optimal for most problems. The calendar basis sets named after the months provide a convergent sequence of partially augmented basis sets that can be used for such calculations. The jun-cc-pV(T+d)Z basis set is very useful for MP2-F12 calculations of barrier heights and hydrogen bond strengths.

show abstract

Section: Wave Function Calculations Of Van Der Waals Potential Curves...mentioning

confidence: 99%

Perspectives on Basis Sets Beautiful: Seasonal Plantings of Diffuse Basis Functions

Papajak

Zheng

et al. 2011

J. Chem. Theory Comput.

Self Cite

665

593

View full text Add to dashboard Cite

show abstract

“…Using these geometries, molecular properties were evaluated at the same level of theory. The 6-31G* basis set has been demonstrated to be well suited for the determination of equilibrium geometries as well as electrostatic potentials and average local ionization energies. ,, However the results of calculations of polarization corrections to the electrostatic potential have been shown to be much more basis set dependent than calculations of the potential itself. , The use of basis sets containing diffuse polarization functions has been recommended. , We experimented therefore with replacing the polarization functions in 6-31G* with more diffuse functions. This generally led to increased magnitudes of P ( r ), especially at distances beyond the van der Waals radii, but did simultaneously decreased the relative differences in P ( r ) between different molecules.…”

Section: Methods and Proceduresmentioning

confidence: 99%

Modified Interaction Properties Function for the Analysis and Prediction of Lewis Basicities

Brinck

1997

J. Phys. Chem. A

View full text Add to dashboard Cite

Ab initio HF/6-31G* electrostatic potentials and average local ionization energies have been computed for 42 nitrogen, oxygen, and sulfur bases. The molecules are characterized by four computed quantities, V min, the spatial minimum in the electrostatic potential, P V min , a polarization correction to V min, Ī S,min, the surface minimum in the average local ionization energy, and Π, a global index derived from the calculated surface electrostatic potential. It is shown that shifts in the O−H stretching frequencies for methanol−base complexes, complexation enthalpies for phenol−base and iodine−base interactions, and gas phase protonation enthalpies can be well correlated to the computed quantities of the bases by a single type of relationship. An analysis of the importance of the different quantities for correlating a specific interaction provides information about the nature of the interaction.

show abstract

“…We have used the RWK2-M model [30] for the intra-and interwater interactions. Less is known about the electron-water interaction [25,31]. We have constructed (Landman et al, Ref.…”

Section: Electron Attachment To Water Clustersmentioning

confidence: 99%

Electron localization in clusters

Landman

Barnett

Cleveland

et al. 1987

Int. J. Quantum Chem.

View full text Add to dashboard Cite

show abstract

Adiabatic Polarization Potentials for the Water and Nitrogen Molecules. A Comparison of Large and Small Basis Sets

Cited by 10 publications

References 42 publications

Perspectives on Basis Sets Beautiful: Seasonal Plantings of Diffuse Basis Functions

Perspectives on Basis Sets Beautiful: Seasonal Plantings of Diffuse Basis Functions

Modified Interaction Properties Function for the Analysis and Prediction of Lewis Basicities

Electron localization in clusters

Contact Info

Product

Resources

About