Intra- and intermolecular interactions in crystals of polar molecules. A study by the mixed quantum mechanical/molecular mechanical SCMP-NDDO method

G. Ferenczy, János G. Ángyán

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Stabilization energies of crystals of polar molecules were calculated with the recently developed NDDO-SCMP method that determines the wave function of a subunit embedded in the symmetrical environment constituted by the copies of the subunit. The total stabilization energies were decomposed into four components. The deformation energy is the difference between the energy of the molecule in the geometries adopted in the crystal on the one hand, and in vacuo, on the other hand. Further energy components are derived from the molecular geometry found in the crystal phase. The electrostatic component is the interaction energy of the molecule with the crystal field, corresponding to the charge distribution obtained in vacuo. The polarization component is the energy lowering resulted in the self-consistent optimization of the wave function in the crystal field. The rest of the stabilization energy is attributed to the dispersion-repulsion component, and is calculated from an empirical potential function. The major novelty of this decomposition scheme is the introduction of the deformation energy. It requires the optimization of the structural parameters, including the molecular geometry, the intermolecular coordinates, and the cell parameters of the crystal. The optimization is performed using the recently implemented forces in the SCMP-NDDO method, and this new feature is discussed in detail. The calculation of the deformation energy is particularly important to obtain stabilization energies for crystals in which the molecular geometry differs considerably from that corresponding to the energy minimum of the isolated molecule. As an example, crystals of diastereoisomeric salts are investigated.

Original languageEnglish
Pages (from-to)1679-1690
Number of pages12
JournalJournal of Computational Chemistry
Volume22
Issue number14
DOIs
Publication statusPublished - Nov 15 2001

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Crystal
Molecules
Crystals
Energy
Interaction
Stabilization
Geometry
Wave functions
Wave Function
Optimization
Charge distribution
Empirical Potential
Electrostatics
Salts
Structural Parameters
Polarization
Potential Function
Decomposition
Salt
Charge

Keywords

  • Crystal stabilization energy calculation
  • Crystal structure prediction
  • Energy decomposition
  • Mixed QM/MM
  • Molecular crystal

ASJC Scopus subject areas

  • Chemistry(all)
  • Safety, Risk, Reliability and Quality

Cite this

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abstract = "Stabilization energies of crystals of polar molecules were calculated with the recently developed NDDO-SCMP method that determines the wave function of a subunit embedded in the symmetrical environment constituted by the copies of the subunit. The total stabilization energies were decomposed into four components. The deformation energy is the difference between the energy of the molecule in the geometries adopted in the crystal on the one hand, and in vacuo, on the other hand. Further energy components are derived from the molecular geometry found in the crystal phase. The electrostatic component is the interaction energy of the molecule with the crystal field, corresponding to the charge distribution obtained in vacuo. The polarization component is the energy lowering resulted in the self-consistent optimization of the wave function in the crystal field. The rest of the stabilization energy is attributed to the dispersion-repulsion component, and is calculated from an empirical potential function. The major novelty of this decomposition scheme is the introduction of the deformation energy. It requires the optimization of the structural parameters, including the molecular geometry, the intermolecular coordinates, and the cell parameters of the crystal. The optimization is performed using the recently implemented forces in the SCMP-NDDO method, and this new feature is discussed in detail. The calculation of the deformation energy is particularly important to obtain stabilization energies for crystals in which the molecular geometry differs considerably from that corresponding to the energy minimum of the isolated molecule. As an example, crystals of diastereoisomeric salts are investigated.",
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AU - Ángyán, János G.

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AB - Stabilization energies of crystals of polar molecules were calculated with the recently developed NDDO-SCMP method that determines the wave function of a subunit embedded in the symmetrical environment constituted by the copies of the subunit. The total stabilization energies were decomposed into four components. The deformation energy is the difference between the energy of the molecule in the geometries adopted in the crystal on the one hand, and in vacuo, on the other hand. Further energy components are derived from the molecular geometry found in the crystal phase. The electrostatic component is the interaction energy of the molecule with the crystal field, corresponding to the charge distribution obtained in vacuo. The polarization component is the energy lowering resulted in the self-consistent optimization of the wave function in the crystal field. The rest of the stabilization energy is attributed to the dispersion-repulsion component, and is calculated from an empirical potential function. The major novelty of this decomposition scheme is the introduction of the deformation energy. It requires the optimization of the structural parameters, including the molecular geometry, the intermolecular coordinates, and the cell parameters of the crystal. The optimization is performed using the recently implemented forces in the SCMP-NDDO method, and this new feature is discussed in detail. The calculation of the deformation energy is particularly important to obtain stabilization energies for crystals in which the molecular geometry differs considerably from that corresponding to the energy minimum of the isolated molecule. As an example, crystals of diastereoisomeric salts are investigated.

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