Item


How does basis set superposition error change the potential surfaces for hydrogen-bonded dimers?

We describe a simple method to automate the geometric optimization of molecular orbital calculations of supermolecules on potential surfaces that are corrected for basis set superposition error using the counterpoise (CP) method. This method is applied to the H-bonding complexes HF/HCN, HF/H2O, and HCCH/H2O using the 6-31G(d,p) and D95 + + (d,p) basis sets at both the Hartree-Fock and second-order Møller-Plesset levels. We report the interaction energies, geometries, and vibrational frequencies of these complexes on the CP-optimized surfaces; and compare them with similar values calculated using traditional methods, including the (more traditional) single point CP correction. Upon optimization on the CP-corrected surface, the interaction energies become more negative (before vibrational corrections) and the H-bonding stretching vibrations decrease in all cases. The extent of the effects vary from extremely small to quite large depending on the complex and the calculational method. The relative magnitudes of the vibrational corrections cannot be predicted from the H-bond stretching frequencies alone

© Journal of Chemical Physics, 1996, vol. 105, núm. 24, p. 11024-11031

American Institute of Physics

Author: Simon i Rabasseda, Sílvia
Duran i Portas, Miquel
Dannenberg, J. J.
Date: 1996
Abstract: We describe a simple method to automate the geometric optimization of molecular orbital calculations of supermolecules on potential surfaces that are corrected for basis set superposition error using the counterpoise (CP) method. This method is applied to the H-bonding complexes HF/HCN, HF/H2O, and HCCH/H2O using the 6-31G(d,p) and D95 + + (d,p) basis sets at both the Hartree-Fock and second-order Møller-Plesset levels. We report the interaction energies, geometries, and vibrational frequencies of these complexes on the CP-optimized surfaces; and compare them with similar values calculated using traditional methods, including the (more traditional) single point CP correction. Upon optimization on the CP-corrected surface, the interaction energies become more negative (before vibrational corrections) and the H-bonding stretching vibrations decrease in all cases. The extent of the effects vary from extremely small to quite large depending on the complex and the calculational method. The relative magnitudes of the vibrational corrections cannot be predicted from the H-bond stretching frequencies alone
Format: application/pdf
Citation: Simon, S., Duran, M., i Dannenberg, J.J. (1996). How does basis set superposition error change the potential surfaces for hydrogen-bonded dimers?. Journal of Chemical Physics, 105 (24), 11024-11031. Recuperat 28 març 2011, a http://link.aip.org/link/doi/10.1063/1.472902
ISSN: 0021-9606 (versió paper)
1089-7690 (versió electrònica)
Document access: http://hdl.handle.net/10256/3309
Language: eng
Publisher: American Institute of Physics
Collection: Reproducció digital del document publicat a: http://dx.doi.org/10.1063/1.472902
Articles publicats (D-Q)
Is part of: © Journal of Chemical Physics, 1996, vol. 105, núm. 24, p. 11024-11031
Rights: Tots els drets reservats
Subject: Anàlisi d’error (Matemàtica)
Energia de superfície
Enllaços químics
Molècules
Optimització matemàtica
Chemical bonds
Error analysis (Mathematics)
Mathematical optimization
Molecules
Molecular orbitals
Orbitals moleculars
Surface energy
Title: How does basis set superposition error change the potential surfaces for hydrogen-bonded dimers?
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

Subjects

Authors


Warning: Unknown: write failed: No space left on device (28) in Unknown on line 0

Warning: Unknown: Failed to write session data (files). Please verify that the current setting of session.save_path is correct (/var/lib/php5) in Unknown on line 0