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Anharmonic excited state frequencies of para-difluorobenzene, toluene and catechol using analytic RI-CC2 second derivatives

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Abstract

Analytic second nuclear derivatives for excited electronic state energies have been implemented for the resolution-of-the-identity accelerated CC2, CIS(D) and ADC(2) models. Our efficient implementation with O(N2) memory demands enables the treatment of medium sized molecules with large basis sets and high numerical precision and thereby paves the way for semi-numerical evaluation of the higher-order derivatives required for anharmonic corrections to excited state vibrational frequencies. We compare CC2 harmonic and anharmonic excited state frequencies with experimental values for para-difluorobenzene, toluene and catechol. Basis set problems occur for out-of-plane bending vibrations due to intramolecular basis set superposition error. For non-planar molecules and in plane modes of planar molecules, the agreement between theory and experiment is better than 30 cm−1 on average and we reassign a number of experimental bands on the basis of the ab initio predictions.

Graphical abstract: Anharmonic excited state frequencies of para-difluorobenzene, toluene and catechol using analytic RI-CC2 second derivatives

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Publication details

The article was received on 08 Nov 2018, accepted on 07 Jan 2019 and first published on 07 Jan 2019


Article type: Paper
DOI: 10.1039/C8CP06952B
Citation: Phys. Chem. Chem. Phys., 2019, Advance Article
  • Open access: Creative Commons BY license
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    Anharmonic excited state frequencies of para-difluorobenzene, toluene and catechol using analytic RI-CC2 second derivatives

    D. P. Tew, C. Hättig and N. K. Graf, Phys. Chem. Chem. Phys., 2019, Advance Article , DOI: 10.1039/C8CP06952B

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