Ground state of naphthyl cation: Singlet or triplet?

We present a benchmark theoretical investigation on the electronic structure and singlet-triplet(S-T) gap of 1- and 2-naphthyl cations using the CCSD(T) method. Our calculations reveal that the ground states of both the naphthyl cations are singlet, contrary to the results obtained by DFT/B3LYP calc...

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Bibliographic Details
Published inThe Journal of chemical physics Vol. 140; no. 11; p. 114312
Main Authors Dutta, Achintya Kumar, Manohar, Prashant U., Vaval, Nayana, Pal, Sourav
Format Journal Article
LanguageEnglish
Published United States American Institute of Physics 21.03.2014
Subjects
Atomic energy levels
CATIONS
ELECTRONIC STRUCTURE
Ground state
GROUND STATES
INCLUSIONS
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
ISOMERS
Mathematical analysis
Physics
TRIPLETS
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Summary:We present a benchmark theoretical investigation on the electronic structure and singlet-triplet(S-T) gap of 1- and 2-naphthyl cations using the CCSD(T) method. Our calculations reveal that the ground states of both the naphthyl cations are singlet, contrary to the results obtained by DFT/B3LYP calculations reported in previous theoretical studies. However, the triplet states obtained in the two structural isomers of naphthyl cation are completely different. The triplet state in 1-naphthyl cation is (π,σ) type, whereas in 2-naphthyl cation it is (σ,σ′) type. The S-T gaps in naphthyl cations and the relative stability ordering of the singlet and the triplet states are highly sensitive to the basis-set quality as well as level of correlation, and demand for inclusion of perturbative triples in the coupled-cluster ansatz.
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ISSN:0021-9606
1089-7690
1089-7690
DOI:10.1063/1.4868485