RT Journal Article
T1 CASPT2 study of the electronic structure and photochemistry of protonated N -nitrosodimethylamine (NDMA-H+ ) at 453 nm
A1 Soto-Martín, Juan
A1 Peláez, Daniel
A1 Algarra-González, Manuel
K1 Química física
AB 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.
PB AIP
YR 2023
FD 2023
LK https://hdl.handle.net/10630/27068
UL https://hdl.handle.net/10630/27068
LA eng
NO Juan Soto, Daniel Peláez, Manuel Algarra; CASPT2 study of the electronic structure and photochemistry of protonated N-nitrosodimethylamine (NDMA-H+) at 453 nm. J. Chem. Phys. 28 May 2023; 158 (20): 204301. https://doi.org/10.1063/5.0147631
NO 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.Funding for open access charge: Universidad de Málaga
DS RIUMA. Repositorio Institucional de la Universidad de Málaga
RD 4 mar 2026