Basis Sets in Quantum Chemistry

Nagy, Balázs; Jensen, Frank

doi:10.1002/9781119356059.ch3

Cited by 83 publications

(90 citation statements)

References 181 publications

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“…It is well-known that the augmentation of basis sets with diffuse functions is essential when calculating higher-order molecular properties, e.g., hyperpolarizabilities. 32 It can be seen in Figure 2 that the augmentation is also necessary for dispersion coefficients and consequently, polarizabilities. There is no apparent benefit of using a basis set beyond aug-cc-pVTZ, therefore this is the basis set of choice in all further calculations in this work.…”

Section: Resultsmentioning

confidence: 99%

Local decomposition of imaginary polarizabilities and dispersion coefficients

Harczuk

Nagy

Jensen

et al. 2017

Phys. Chem. Chem. Phys.

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We present a new way to compute the two-body contribution to the dispersion energy using ab initio theory. By combining the complex polarization propagator method and the LoProp transformation, local contributions to the Casimir-Polder interaction is obtained. The full dispersion energy in dimer systems consisting of pairs of molecules including H 2 , N 2 , CO, CH 4 , pyridine, and benzene is investigated, where anisotropic as well as isotropic models of dispersion are obtained using a decomposition scheme for the dipole-dipole polarizability. It is found that the local minima structure of the π-cloud stacking of the benzene dimer is underestimated by the total molecular dispersion, but is alleviated by the inclusion of atomic interactions via the decomposition scheme. The dispersion energy in the T-shaped benzene dimer system is greatly underestimated by all dispersion models, as compared to high-level quantum calculations.The generalization of the decomposition scheme to higher order multipole polarizability interactions, representing higher order dispersion coefficients, is briefly discussed. It is argued that the incorporation of atomic C 6 coefficients in new atomic force fields may have important ramifications in molecular dynamics studies of biomolecular systems.

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Section: Resultsmentioning

confidence: 99%

Local decomposition of imaginary polarizabilities and dispersion coefficients

Harczuk

Nagy

Jensen

et al. 2017

Phys. Chem. Chem. Phys.

Self Cite

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“…For a double-ζ quality regular basis we found that for complementing the functions with maximum angular momentum l max an additional function with an exponent of ∼ 0.3 is best, while for functions with angular momenta l max + 1 and l max + 2, exponents of ∼ 1.0 recover the most energy in agreement with general rules for basis set construction. 81 If several functions with l max + 1 and l max + 2 are added, exponents of 1.0 and above are preferable.…”

Section: Automatic Generation Of Auxiliary Basis Setsmentioning

confidence: 99%

On Resolution-of-the-Identity Electron Repulsion Integral Approximations and Variational Stability

Wirz

Reine

Pedersen

2017

J. Chem. Theory Comput.

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The definiteness of the Mulliken and Dirac electron repulsion integral (ERI) matrices is examined for different classes of resolution-of-the-identity (RI) ERI approximations with particular focus on local fitting techniques. For global RI, robust local RI, and nonrobust local RI we discuss the definiteness of the approximated ERI matrices as well as the resulting bounds of Hartree, exchange, and total energies. Lower bounds of Hartree and exchange energy contributions are crucial as their absence may lead to variational instabilities, causing severe convergence problems or even convergence to a spurious state in self-consistent-field optimizations. While the global RI approximation guarantees lower bounds of Hartree and exchange energies, local RI approximations are generally unbounded. The robust local RI approximation guarantees a lower bound of the exchange energy but not of the Hartree energy. The nonrobust local RI approximation guarantees a lower bound of the Hartree energy but not of the exchange energy. These issues are demonstrated by sample calculations on carbon dioxide and benzene using the pair atomic RI approximation.

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“…Nowadays, standardized basis set libraries are not commonly available for solids as they are for molecules, 13 , 14 despite recent attempts in that direction being carried out by Bredow and co-workers. 15 − 17 The reasons are not only to be ascribed to a lesser effort in a systematic construction of all-purpose basis sets but also more specifically to the wide difference in chemical bonding as outlined above.…”

Section: Introductionmentioning

confidence: 99%

Gaussian Basis Sets for Crystalline Solids: All-Purpose Basis Set Libraries vs System-Specific Optimizations

Daga

Civalleri

Maschio

2020

J. Chem. Theory Comput.

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It is customary in molecular quantum chemistry to adopt basis set libraries in which the basis sets are classified according to either their size (triple-ζ, quadruple-ζ, ...) and the method/property they are optimal for (correlation-consistent, linear-response, ...) but not according to the chemistry of the system to be studied. In fact the vast majority of molecules is quite homogeneous in terms of density (i.e., atomic distances) and types of bond involved (covalent or dispersive). The situation is not the same for solids, in which the same chemical element can be found having metallic, ionic, covalent, or dispersively bound character in different crystalline forms or compounds, with different packings. This situation calls for a different approach to the choice of basis sets, namely a system-specific optimization of the basis set that requires a practical algorithm that could be used on a routine basis. In this work we develop a basis set optimization method based on an algorithm–similar to the direct inversion in the iterative subspace–that we name BDIIS. The total energy of the system is minimized together with the condition number of the overlap matrix as proposed by VandeVondele et al. [ J. Chem. Phys. 2007 227 114105 ]. The details of the method are here presented, and its performance in optimizing valence orbitals is shown. As demonstrative systems we consider simple prototypical solids such as diamond, graphene sodium chloride, and LiH, and we show how basis set optimizations have certain advantages also toward the use of large (quadruple-ζ) basis sets in solids, both at the DFT and Hartree–Fock level.

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Basis Sets in Quantum Chemistry

Cited by 83 publications

References 181 publications

Local decomposition of imaginary polarizabilities and dispersion coefficients

Local decomposition of imaginary polarizabilities and dispersion coefficients

On Resolution-of-the-Identity Electron Repulsion Integral Approximations and Variational Stability

Gaussian Basis Sets for Crystalline Solids: All-Purpose Basis Set Libraries vs System-Specific Optimizations

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