An MS-CASPT2 Calculation of the Excited Electronic States of an Axial Difluoroborondipyrromethene (BODIPY) Dimer

Journal Article · Wed Jun 06 00:00:00 UTC 2018 · Journal of Chemical Theory and Computation

DOI: https://doi.org/10.1021/acs.jctc.8b00136 · OSTI ID:1688392

Wen, Jin ^[1]; Han, Bowen ^[2]; Havlas, Zdeněk ^[3]; Michl, Josef  ^[4]

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1. Institute of Organic Chemistry and Biochemistry, AS CR, Prague (Czech Republic); University of Colorado
2. Univ. of Colorado, Boulder, CO (United States)
3. Institute of Organic Chemistry and Biochemistry, AS CR, Prague (Czech Republic)
4. Institute of Organic Chemistry and Biochemistry, AS CR, Prague (Czech Republic); Univ. of Colorado, Boulder, CO (United States)

The previously reported (Duman et al., J. Org. Chem. 2012, 77, 4516) calculated state energies of monomeric difluoroborondipyrromethene (BODIPY) and its axial dimer would suggest that these dyes are promising candidates for singlet fission, and the dimer was computed to have an unusual low-lying doubly excited state. We find that these results were affected by the use of an imbalanced active space in multireference calculations and are not correct. Multistate complete-active-space second-order perturbation theory (MS-CASPT2/cc-pVDZ) calculations using an [8,8] (8 electrons in 8 orbitals) active space for the monomer and a [16,16] active space for the dimer reproduce quite well the observed excitation energies of the S₁ states of both, and yield T₁ excitation energies well in excess of half of the S₁ excitation energies. We conclude that neither BODIPY monomer nor its axial dimer would permit exothermic singlet fission and are not worthy of investigation as potentially useful candidates, and that the unusual low-energy doubly excited states of the dimer were artifacts.

• Research Organization: Univ. of Colorado, Boulder, CO (United States)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES)
• Grant/Contract Number: SC0007004
• OSTI ID: 1688392
• Journal Information: Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 8 Vol. 14; ISSN 1549-9618
• Publisher: American Chemical SocietyCopyright Statement
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Basis sets
Chemical calculations
Energy
Excited states
Wave function