Although coupled cluster theory coupled to large basis sets can reach impressive accuracies for thermochemical and spectroscopic properties, it is still limited to small/medium sized molecules. Density functional theory (DFT) represents the working option for systems composed of hundreds to thousands heavy atoms. In this context, investigations are required aimed at characterizing the performances of the different density functionals (DF). This work focuses on the study of DFT performances in the prediction of spectroscopic properties, with particular attention to the vibrational problem, by focusing on the CH2F2 molecule as a test case. An extensive and systematic investigation is performed on several DFT model chemistries by testing their predictions of molecular constants and vibrational frequencies and intensities against CCSD(T)/ aug-cc-pCVQZ data. B3LYP, B3PW91, B97-1, PBE0, TPSSh, M05, M05-2X, and B2PLYP DFs are used in conjunction with a variety of basis sets. Anharmonic frequencies are derived from the VPT2 treatment of anharmonic- and hybrid CCSD(T)/DFTforce fields.

What are the spectroscopic properties of HFC-32? Answers from DFT

TASINATO, Nicola
2014

Abstract

Although coupled cluster theory coupled to large basis sets can reach impressive accuracies for thermochemical and spectroscopic properties, it is still limited to small/medium sized molecules. Density functional theory (DFT) represents the working option for systems composed of hundreds to thousands heavy atoms. In this context, investigations are required aimed at characterizing the performances of the different density functionals (DF). This work focuses on the study of DFT performances in the prediction of spectroscopic properties, with particular attention to the vibrational problem, by focusing on the CH2F2 molecule as a test case. An extensive and systematic investigation is performed on several DFT model chemistries by testing their predictions of molecular constants and vibrational frequencies and intensities against CCSD(T)/ aug-cc-pCVQZ data. B3LYP, B3PW91, B97-1, PBE0, TPSSh, M05, M05-2X, and B2PLYP DFs are used in conjunction with a variety of basis sets. Anharmonic frequencies are derived from the VPT2 treatment of anharmonic- and hybrid CCSD(T)/DFTforce fields.
Computational spectroscopy; Density functional theory; Difluoromethane; Hybrid CCSD(T)/DFT force fields; VPT2 software
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11384/66179
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