Artículo
UV Photofragmentation of Cold Cytosine-M+ Complexes (M+: Na+, K+, Ag+)
Taccone, Martín Ignacio
; Cruz Ortiz, Andres Felipe
; Dezalay, Jordan; Soorkia, Satchin; Broquier, Michel; Grégoire, Gilles; Sanchez, Cristian Gabriel
; Pino, Gustavo Ariel
![Icon](/themes/CONICETDigital/images/conicet.png)
![Icon](/themes/CONICETDigital/images/conicet.png)
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Fecha de publicación:
09/2019
Editorial:
American Chemical Society
Revista:
Journal of Physical Chemistry A
ISSN:
1089-5639
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
The UV photofragmentation spectra of cold cytosine-M+ complexes (M+: Na+, K+, Ag+) were recorded and analyzed through comparison with geometry optimizations and frequency calculations of the ground and excited states at the SCS-CC2/Def2-SVPD level of theory. While in all complexes, the ground state minimum geometry is planar (Cs symmetry), the ππ∗ state minimum geometry has the NH2 group slightly twisted and an out-of-plane metal cation. This was confirmed by comparing the simulated ππ∗ Franck-Condon spectra with the vibrationally resolved photofragmentation spectra of CytNa+ and CytK+. Vertical excitation transitions were also calculated to evaluate the energies of the CT states involving the transfer of an electron from the Cyt moiety to M+. For both CytK+ and CytNa+ complexes, the first CT state corresponds to an electron transfer from the cytosine aromatic πring to the antibonding σ∗ orbital centered on the alkali cation. This πσ∗ state is predicted to lie much higher in energy (>6 eV) than the band origin of the π-π∗ electronic transition (around 4.3 eV) unlike what is observed for the CytAg+ complex for which the first excited state has a nOσ∗ electronic configuration. This is the reason for the absence of the Cyt+ + M charge transfer fragmentation channel for CytK+ and CytNa+ complexes.
Palabras clave:
DNA
,
Cytosine
,
UV Photofragmentation
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Articulos(INFIQC)
Articulos de INST.DE INVESTIGACIONES EN FISICO- QUIMICA DE CORDOBA
Articulos de INST.DE INVESTIGACIONES EN FISICO- QUIMICA DE CORDOBA
Citación
Taccone, Martín Ignacio; Cruz Ortiz, Andres Felipe; Dezalay, Jordan; Soorkia, Satchin; Broquier, Michel; et al.; UV Photofragmentation of Cold Cytosine-M+ Complexes (M+: Na+, K+, Ag+); American Chemical Society; Journal of Physical Chemistry A; 123; 36; 9-2019; 7744-7750
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