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Anharmonic excited state frequencies of para-difluorobenzene, toluene and catechol using analytic RI-CC2 second derivatives.
- Source :
-
Physical chemistry chemical physics : PCCP [Phys Chem Chem Phys] 2019 Jul 14; Vol. 21 (26), pp. 14063-14072. Date of Electronic Publication: 2019 Jan 18. - Publication Year :
- 2019
-
Abstract
- Analytic second nuclear derivatives for excited electronic state energies have been implemented for the resolution-of-the-identity accelerated CC2, CIS(D <subscript>∞</subscript> ) and ADC(2) models. Our efficient implementation with O(N <superscript>2</superscript> ) 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 <superscript>-1</superscript> on average and we reassign a number of experimental bands on the basis of the ab initio predictions.
Details
- Language :
- English
- ISSN :
- 1463-9084
- Volume :
- 21
- Issue :
- 26
- Database :
- MEDLINE
- Journal :
- Physical chemistry chemical physics : PCCP
- Publication Type :
- Academic Journal
- Accession number :
- 30656295
- Full Text :
- https://doi.org/10.1039/c8cp06952b