TY - JOUR
T1 - Accurate calculation of vibrational frequencies using explicitly correlated coupled-cluster theory
AU - Rauhut, Guntram
AU - Knizia, Gerald
AU - Werner, Hans Joachim
N1 - Funding Information:
This work was funded in the priority program 1145 (Modern and universal first-principles methods for many-electron systems in chemistry and physics) by the Deutsche Forschungsgemeinschaft. We thank Professor T. Hrenar for his contributions to the implementation of the surface generation code. H.-J.W. was also grateful for generous support by the Fonds der Chemischen Industrie.
PY - 2009
Y1 - 2009
N2 - The recently proposed explicitly correlated CCSD (T) -F12x (x=a,b) approximations [T. B. Adler, G. Knizia, and H.-J. Werner, J. Chem. Phys. 127, 221106 (2007)] are applied to compute equilibrium structures and harmonic as well as anharmonic vibrational frequencies for H2 O, HCN, CO2, CH2 O, H2 O2, C2 H2, CH2 NH, C2 H2 O, and the trans-isomer of 1,2- C2 H2 F2. Using aug-cc-pVTZ basis sets, the CCSD(T)-F12a equilibrium geometries and harmonic vibrational frequencies are in very close agreement with CCSD(T)/aug-cc-pV5Z values. The anharmonic frequencies are evaluated using vibrational self-consistent field and vibrational configuration interaction methods based on automatically generated potential energy surfaces. The mean absolute deviation of the CCSD(T)-F12a/aug-cc-pVTZ anharmonic frequencies from experimental values amounts to only 4.0 cm-1.
AB - The recently proposed explicitly correlated CCSD (T) -F12x (x=a,b) approximations [T. B. Adler, G. Knizia, and H.-J. Werner, J. Chem. Phys. 127, 221106 (2007)] are applied to compute equilibrium structures and harmonic as well as anharmonic vibrational frequencies for H2 O, HCN, CO2, CH2 O, H2 O2, C2 H2, CH2 NH, C2 H2 O, and the trans-isomer of 1,2- C2 H2 F2. Using aug-cc-pVTZ basis sets, the CCSD(T)-F12a equilibrium geometries and harmonic vibrational frequencies are in very close agreement with CCSD(T)/aug-cc-pV5Z values. The anharmonic frequencies are evaluated using vibrational self-consistent field and vibrational configuration interaction methods based on automatically generated potential energy surfaces. The mean absolute deviation of the CCSD(T)-F12a/aug-cc-pVTZ anharmonic frequencies from experimental values amounts to only 4.0 cm-1.
UR - https://www.scopus.com/pages/publications/59949104962
UR - https://www.scopus.com/pages/publications/59949104962#tab=citedBy
U2 - 10.1063/1.3070236
DO - 10.1063/1.3070236
M3 - Article
C2 - 19206956
AN - SCOPUS:59949104962
SN - 0021-9606
VL - 130
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 5
M1 - 054105
ER -