Research output: Contribution to journal › Article › peer-review
Primary photophysical and photochemical processes for cerium ammonium nitrate (CAN) in acetonitrile. / Fedunov, Roman G.; Pozdnyakov, Ivan P.; Mikheylis, Aleksander V. et al.
In: Photochemical and Photobiological Sciences, Vol. 23, No. 4, 04.2024, p. 781-792.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Primary photophysical and photochemical processes for cerium ammonium nitrate (CAN) in acetonitrile
AU - Fedunov, Roman G.
AU - Pozdnyakov, Ivan P.
AU - Mikheylis, Aleksander V.
AU - Melnikov, Alexei A.
AU - Chekalin, Sergei V.
AU - Glebov, Evgeni M.
N1 - The financial support of the Russian Science Foundation (Grant № 23-13-00226) is gratefully acknowledged.
PY - 2024/4
Y1 - 2024/4
N2 - Cerium ammonium nitrate (CAN) is an important photolytic source of NO3• radicals in aqueous nitric acid solutions and in acetonitrile. In this work we performed the study of primary photochemical processes for CAN in acetonitrile by means of ultrafast TA spectroscopy and quantum chemical calculations. Photoexcitation of CAN is followed by ultrafast (< 100 fs) intersystem crossing; the vibrationally cooled triplet state decays to pentacoordinated Ce(III) intermediate and NO3• radical with the characteristic time of ca. 40 ps. Quantum chemical (QM) calculations satisfactorily describe the UV–vis spectrum of the triplet state. An important feature of CAN photochemistry in CH3CN is the partial stabilization of the radical complex (RC) [(NH4)2CeIII(NO3)5…NO3•], which lifetime is ca. 2 μs. The possibility of the RC stabilization is supported by the QM calculations. Graphical abstract: (Figure presented.)
AB - Cerium ammonium nitrate (CAN) is an important photolytic source of NO3• radicals in aqueous nitric acid solutions and in acetonitrile. In this work we performed the study of primary photochemical processes for CAN in acetonitrile by means of ultrafast TA spectroscopy and quantum chemical calculations. Photoexcitation of CAN is followed by ultrafast (< 100 fs) intersystem crossing; the vibrationally cooled triplet state decays to pentacoordinated Ce(III) intermediate and NO3• radical with the characteristic time of ca. 40 ps. Quantum chemical (QM) calculations satisfactorily describe the UV–vis spectrum of the triplet state. An important feature of CAN photochemistry in CH3CN is the partial stabilization of the radical complex (RC) [(NH4)2CeIII(NO3)5…NO3•], which lifetime is ca. 2 μs. The possibility of the RC stabilization is supported by the QM calculations. Graphical abstract: (Figure presented.)
KW - Cerium ammonium nitrate (CAN)
KW - Photochemistry
KW - Quantum chemical calculations
KW - Ultrafast TA spectroscopy
KW - •NO3 radical
UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85188947084&origin=inward&txGid=0ef4ff3c9e0dff9ca930bb6d7338d7a9
UR - https://www.mendeley.com/catalogue/2324c5ec-10bf-3d01-8f4d-acbd1a66ea8a/
U2 - 10.1007/s43630-024-00554-1
DO - 10.1007/s43630-024-00554-1
M3 - Article
C2 - 38546955
VL - 23
SP - 781
EP - 792
JO - Photochemical and Photobiological Sciences
JF - Photochemical and Photobiological Sciences
SN - 1474-905X
IS - 4
ER -
ID: 61083345