Optical properties of irradiated imidazolium based room temperature ionic liquids: new microscopic insights into the radiation induced mutations
文献信息
Apurav Guleria, Ajay K Singh, Soumyakanti Adhikari
Considering the future perspectives of room temperature ionic liquids (RTILs) in areas involving high radiation fields (such as the nuclear fuel cycle and space applications), it is essential to probe and have a microscopic understanding of the radiation induced perturbations in the molecular structures and the intrinsic bonding interactions existing in the ILs. Herein, a focused investigation concerning the photophysical behavior of post-irradiated FAP (fluoroalkyl phosphate) imidazolium ILs revealed considerable rearrangements and bonding realignments of the ionic moieties in the ILs on irradiation, however, their physicochemical properties do not change significantly even at high absorbed doses. Most interestingly, the well-established excitation wavelength dependent fluorescence (FL) behavior of the ILs was considerably perturbed on irradiation and this is attributed to the radiation induced decoupling of pre-existing different associated structures of ions, and the subsequent formation of oligomers and other species containing multiple bond order groups. This was further substantiated by vibrational studies, where peaks appearing in the range 1600–1800 cm−1 indicated the formation of double bonded products. Furthermore, for the hydroxyl functionalized (in the alkyl side chain of the imidazolium cation) IL, a blue shift in the O–H stretching frequency was observed for the –OH group H-bonded to the FAP anion (νOH⋯[FAP]−), while a red shift was observed for the H-bonded –OH groups in the cationic clusters. The FL lifetime values were found to increase with irradiation, which clearly indicates the enhancement in the rigidity level in the vicinity of the ions, thereby hindering the non-radiative decay processes. Such studies could contribute to the fundamental understanding of the radiation driven perturbations in the structure–property relationships, which eventually affect the radiolytic degradation pathways and the product distribution in RTILs.
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Russian Chemical Bulletin

Journal of Saudi Chemical Society

Chemical Communications

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Chemistry Education Research and Practice

New Journal of Chemistry

Acta Materialia

Current Opinion in Colloid & Interface Science

Russian Journal of Applied Chemistry

Russian Journal of General Chemistry
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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