Assessing the Accuracy of SAPT(DFT) Interaction Energies by Comparison with Experimentally Derived Noble Gas Potentials and Molecular Crystal Lattice Energies

Abstract

The density functional version of symmetry-adapted perturbation theory, SAPT(DFT), is a computationally efficient method for calculating intermolecular interaction energies. We evaluate its accuracy by comparison with experimentally determined noble gas interaction potentials and sublimation enthalpies, most of which have not been previously calculated using this method. In order to compare the results with wavefunction methods, we also calculate these quantities using MP2 and, for noble gas dimers, using CCSD(T). For the crystal lattice energy calculations, we include corrections to the dispersion, electrostatic, and induction energies that account for the finite interaction distance cutoff and higher-order induction contributions. Overall, the energy values extrapolated to the complete basis set limit show that SAPT(DFT) achieves significantly better agreement with experiment than MP2.

Importance of Nonclassical σ-Hole Interactions for the Reactivity of λ3-Iodane Complexes

“…The interaction energies between monomers in an adduct were obtained using wave function-based SAPT as implemented in the open source PSI4 electronic structure package . The SAPT approach allows the decomposition of the interaction energy into components such as electrostatic, exchange, induction, and dispersion . For the SAPT analysis, we used the def2-pvtz-PP basis sets, including the ECP recently implemented for iodine in PSI4.…”

Physical nature of silane⋯carbene dimers revealed by state‐of‐the‐art ab initio calculations

“…The CCSD(T) method occupies a special place in computational chemistry because it is considered as the gold standard. [15][16][17][18] It results from the fact that using this method one can get (at a great cost) very accurate values of many properties, including interaction energies. Therefore, our discussion about the strength of the silaneÁ Á Ácarbene dimers will be started with reference to the appropriate numerical values obtained using this method (see the last column in Table 2).…”

“…This is the main purpose of this article. The next one is to calculate the interaction energy itself, using the very accurate CCSD(T) method currently considered as the gold standard of computational chemistry [15][16][17][18] and other ab initio methods. square, respectively, and 0.000060 and 0.000040 for maximum displacement and its root mean square, respectively), and integration grid was increased to the (99, 590) one (UltraFine in Gaussian 09 [19] ) having 99 radial shells and 590 angular points per shell.…”

Structural transitions in mixed ternary noble gas clusters

“…Many studies have traced the structural growth patterns of atomic clusters of different sizes to study their properties. Experimental and theoretical studies implied that the structure of noble gas clusters is icosahedral at small size and undergoes a direct transition to being face centered cubic (fcc) with increasing size [2][3][4]. Clusters of argon, krypton, and xenon are grown in a free jet and ionized by electron impact, and pronounced "magic numbers" in the distributions of large cluster ions occur at sizes of 147 (148 for Ar), 309, and 561 [5].…”