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      XH-stretching overtone transitions calculated using explicitly correlated coupled cluster methods

      Lane, Joseph R.; Kjaergaard, Henrik G.
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      Lane XH-stretching overtone transitions.pdf
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      DOI
       10.1063/1.3408192
      Link
       jcp.aip.org
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      Lane, J.R. & Kjaergaard, H.G. (2010). XH-stretching overtone transitions calculated using explicitly correlated coupled cluster methods. The Journal of Chemical Physics, 132, 174304.
      Permanent Research Commons link: https://hdl.handle.net/10289/3888
      Abstract
      We have calculated XH-stretching (where X=O, C, F, Cl) fundamental and overtone transitions for three diatomics and a few small molecules using a local mode model. The potential energy curves and dipole moment functions are calculated using the recently developed explicitly correlated coupled cluster with single doubles and perturbative triples theory [CCSD_T_-F12] with the associated VXZ-F12 (where X=D, T, Q) basis sets. We find that the basis set convergence of calculated frequencies and oscillator strengths obtained with the explicitly correlated method is much more rapid than with conventional CCSD(T) and the Dunning type correlation consistent basis sets. Furthermore, CCSD(T)-F12 frequencies and oscillator strengths obtained with the VTZ-F12 and VQZ-F12 basis sets are found to be in excellent agreement with the CCSD(T) complete basis set limit. We find that comparison of CCSD(T)-F12 frequencies with experiment is less good. The inclusion of explicit correlation exposes the inherent error of the CCSD(T) method to overestimate vibrational frequencies, which is normally compensated by basis set incompleteness error. As a consequence, we suggest that conventional CCSD(T) in combination with the aug-cc-pVTZ or aug-cc-pVQZ basis sets is likely to yield calculated XH-stretching frequencies in closest agreement with experiment.
      Date
      2010
      Type
      Journal Article
      Publisher
      American Institute of Physics
      Rights
      This article has been published in the journal: The Journal of Chemical Physics. © 2010 American Institute of Physics.
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