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


Autoria(s): Simon i Rabasseda, Sílvia; Duran i Portas, Miquel; Dannenberg, J. J.
Data(s)

1996

Resumo

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

Formato

application/pdf

Identificador

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

0021-9606 (versió paper)

1089-7690 (versió electrònica)

http://hdl.handle.net/10256/3309

http://dx.doi.org/10.1063/1.472902

Idioma(s)

eng

Publicador

American Institute of Physics

Relação

Reproducció digital del document publicat a: http://dx.doi.org/10.1063/1.472902

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

Articles publicats (D-Q)

Direitos

Tots els drets reservats

Palavras-Chave #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
Tipo

info:eu-repo/semantics/article