Energy Decomposition Analyses for Many-Body Interaction and Applications to Water Complexes

Abstract

Two algorithms for many-body interaction energy decomposition within the Hartree−Fock approximation are presented. These two schemes, which are extensions of the two-body Kitaura−Morokuma (KM) analysis and the reduced variational space self-consistent-field (RVS SCF) method, decompose the interaction energy into electrostatic, exchange, polarization, and charge transfer components. The Hartree-Fock interaction energies for the optimum water dimer, trimer, and tetramer were analyzed in terms of two-, three-, and fourbody terms of these individual components. Counterpoise calculations of the exchange and charge transfer components proposed by Tomasi were performed to estimate the basis set superposition errors. The results show that the three-body nonadditive terms of water trimer and tetramer are dominated by the polarization and charge transfer components at their optimized structures with various basis sets and that the four-body term of water tetramer is very small. The RVS SCF energy components, whose corresponding wave functions obey the Pauli exclusion principle, are better behaved than their counterparts in the KM analysis when the orbital interactions are strong. Disciplines Chemistry CommentsReprinted (adapted) ReceiVed: March 6, 1996; In Final Form: May 23, 1996 X Two algorithms for many-body interaction energy decomposition within the Hartree-Fock approximation are presented. These two schemes, which are extensions of the two-body Kitaura-Morokuma (KM) analysis and the reduced variational space self-consistent-field (RVS SCF) method, decompose the interaction energy into electrostatic, exchange, polarization, and charge transfer components. The Hartree-Fock interaction energies for the optimum water dimer, trimer, and tetramer were analyzed in terms of two-, three-, and fourbody terms of these individual components. Counterpoise calculations of the exchange and charge transfer components proposed by Tomasi were performed to estimate the basis set superposition errors. The results show that the three-body nonadditive terms of water trimer and tetramer are dominated by the polarization and charge transfer components at their optimized structures with various basis sets and that the four-body term of water tetramer is very small. The RVS SCF energy components, whose corresponding wave functions obey the Pauli exclusion principle, are better behaved than their counterparts in the KM analysis when the orbital interactions are strong.

Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies

“…Natural bond orbital (NBO) 75 and natural EDA 38 suggests that CT is predominant 39,40,76 because if CT is neglected, NBO analysis shows no binding at the water dimer equilibrium geometry. However, other earlier decomposition methods [33][34][35][36][37] estimated that CT contributes only around 20% of the overall binding energy 34,35,77 .…”

“…• Unlike earlier decomposition methods [33][34][35][36][37][38][39][40] , ALMO EDA and CTA treat the polarization term in a variationally optimal way. Therefore, CT effects (i.e.…”

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

“…approaches 19,59 and the linear-scaling EDA of Phipps et al 60 ) and their ability to treat many-fragment systems, 61 they are instrumental in the continuing effort to better understand liquid water and ice, [62][63][64] cooperative effects, 25,[65][66][67][68] and other interactions in solution. 69,70 Moreover, they treat both inter-and intramolecular 18,19,43,71 (including through-bond) interactions on equal footing (including through bond) and, thus, capably describe phenomena that are of a mixed or non-covalent nature, e.g., dative bonds, 27,72,73 as well as chemisorption and physisorption processes 221,222 (through a "periodic EDA" by Tonner et al 223 ).…”

Energy decomposition analysis of covalent bonds and intermolecular interactions

“…EDA methods have been extended to study manybody systems, as was done by Chen and Gordon. 8 There are many HF EDA algorithms such as the natural energy decomposition analysis ͑NEDA͒, 9 the constrained space orbital variation, 10 the reduced variational space ͑RVS͒ analysis, 8,11 the block-localized wavefunction EDA, 12 and the absolutely localized molecular orbital EDA. 13 In order to complete the interaction analysis, additional supermolecule MP2 or CCSD͑T͒ calculations are often performed to derive the dispersion energy for these HF based methods.…”