CASPT2 study of the electronic structure and photochemistry of protonated N-nitrosodimethylamine (NDMA-H+) at 453 nm
Fecha
2023Versión
Acceso abierto / Sarbide irekia
Tipo
Artículo / Artikulua
Versión
Versión aceptada / Onetsi den bertsioa
Identificador del proyecto
AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-122613OB-I00
Impacto
|
10.1063/5.0147631
Resumen
In this work, we have studied the photodissociation of the protonated derivatives of N-nitrosodimethylamine [(CH3)2N–NO] with the
CASPT2 method. It is found that only one of the four possible protonated species of the dialkylnitrosamine compound absorbs in the visible region at 453 nm, that is, N-nitrosoammonium ion [(CH3)2NH-NO]+
. This species is also the only one whose first singlet excited ...
[++]
In this work, we have studied the photodissociation of the protonated derivatives of N-nitrosodimethylamine [(CH3)2N–NO] with the
CASPT2 method. It is found that only one of the four possible protonated species of the dialkylnitrosamine compound absorbs in the visible region at 453 nm, that is, N-nitrosoammonium ion [(CH3)2NH-NO]+
. This species is also the only one whose first singlet excited state
is dissociative to directly yield the aminium radical cation [(CH3)2NHN⋅]
+
and nitric oxide. In addition, we have studied the intramolecular proton migration reaction {[(CH3)2N–NOH]
+ → [(CH3)2NH–NO]+
} both in the ground and excited state (ESIPT/GSIPT); our results
indicate that this process is not accessible neither in the ground nor in the first excited state. Furthermore, as a first approximation,
MP2/HF calculations on the nitrosamine–acid complex indicate that in acidic solutions of aprotic solvents, only [(CH3)2NH–NO]+
is
formed. [--]
Materias
Protonated N-nitrosodimethylamine (NDMA-H+),
CASPT2 method,
N-nitrosoammonium ion,
Intramolecular proton migration reaction
Editor
American Institute of Physics
Publicado en
Journal of Chemical Physics, 158, 204301 (2023)
Departamento
Universidad Pública de Navarra. Departamento de Ciencias /
Nafarroako Unibertsitate Publikoa. Zientziak Saila /
Universidad Pública de Navarra/Nafarroako Unibertsitate Publikoa. Institute for Advanced Materials and Mathematics - INAMAT2
Versión del editor
Entidades Financiadoras
This work was supported by the Spanish Ministry of Science
and Innovation (Grant No. MCIN/AEI/10.13039/501100011033)
through Project No. PID2021-122613OB-I00.