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 -