Abstract
The properties of formamide, its protonated form and interaction complexes with lithium and sodium cations were studied in electronically excited singlet states by means of high-level multireference ab initio methods. The vertical excitation energies show a marked influence on protonation with particular large effects found for the O-protonated form as compared to neutral formamide. Complexation with Li+ and Na+ leads to a pronounced shift of the nO–π* state to higher energies while the π–π* state moves in opposite direction. Geometry optimizations in the lowest excited singlet show strong geometrical effects leading to pyramidalization at the N and C atoms. The photodynamical simulations performed for formamide in the first excited singlet state show that the main primary deactivation path is CN dissociation with a lifetime of about 420 fs.
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Antol I, Eckert-Maksić M, Barbatti M, Lischka H (2007) J Chem Phys, in print
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Correspondence: Mirjana Eckert-Maksić, Division of Organic Chemistry and Biochemistry, Rudjer Bošković Institute, P.O.B. 180, HR-10002 Zagreb, Croatia; Hans Lischka, Institute for Theoretical Chemistry, University of Vienna, Währingerstrasse 17, A-1090 Vienna, Austria.
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Antol, I., Barbatti, M., Eckert-Maksić, M. et al. Quantum chemical calculations of electronically excited states: formamide, its protonated form and alkali cation complexes as case studies. Monatsh Chem 139, 319–328 (2008). https://doi.org/10.1007/s00706-007-0803-2
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DOI: https://doi.org/10.1007/s00706-007-0803-2