Approximating coupled cluster level vibrational frequencies with composite methods.
An extensive study of the harmonic frequencies of a large set of small polyatomic closed-shell molecules computed at both single level ab initio and composite approximations is presented here. Using various combinations of basis sets, composite methods are capable of predicting single level ab initio CCSD(T) harmonic frequencies to within 5 cm(-1) on average, which suggests a computationally affordable means of obtaining highly accurate vibrational frequencies compared to the CCSD(T) level. A general approach for calculating the composite level equilibrium geometries and harmonic frequencies for polyatomic systems that uses the Collin's method of interpolating potential energy surfaces is also described here. This approach is further tested on tetrafluoromethane, and an estimation of the potential CPU time savings that may be obtained is also presented. It is envisaged that the findings here will enable theoretical studies of fundamental frequencies and energetics of significantly larger molecular systems.
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543.
Yanping
Y
Fan
Junming
J
Ho
Ryan P A
RP
Bettens