2026-06-02T22:33:14Zhttps://riuma.uma.es/rest/oai/request

oai:riuma.uma.es:10630/270682026-02-03T11:27:55Zcom_10630_2254col_10630_37953

CASPT2 study of the electronic structure and photochemistry of protonated N -nitrosodimethylamine (NDMA-H+ ) at 453 nm Soto-Martín, Juan Peláez, Daniel Algarra-González, Manuel Química física 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. 2023-06-26T10:22:53Z 2023-06-26T10:22:53Z 2023 journal article 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 https://hdl.handle.net/10630/27068 https://doi.org/10.1063/5.0147631 eng http://creativecommons.org/licenses/by/4.0/ open access Atribución 4.0 Internacional AIP