caa a22 4500 475761472 CHVBK 20180406123552.0 cr unu---uuuuu 170329e20000501xx s 000 0 eng 10.1007/BF02494704 doi (NATIONALLICENCE)springer-10.1007/BF02494704 Reactions of photogenerated fluorine atoms with molecules trapped in solid argon [Elektronische Daten] 3. Formation of stabilized.NH2 radicals and.NH2−HF radical-molecule complexes in the reactions of fluorine atoms with NH3 molecules [E. Misochko, I. Gol'dshleger, A. Akimov] Isolated radicals.NH2 and radical-molecule complexes.NH2−HF, which are products of the reactions of mobile fluorine atoms with NH3 molecules in solid argon, were identified by EPR spectroscopy. The isotropic HFC constants of the complex (a N=1.20,a H=2.40, anda F=0.70 mT) were determined experimentally. The constant of isotropic HFC with the nucleus of hydrogen atom of the HF molecule is less than 0.1 mT. This assignment was confirmed in the experiments on isotope substitution of atoms (H→D),14N→15N) in the NH3 molecule. According to quantum-chemical calculations, the free complex.NH2−HF has a planar structure withC 2, summetry and a binding energy of 12 kcal mol−1. Optimization of the arrangement of the complex in the crystal showed that its structure is only slightly distorted in the Ar lattice so that the equilibrium configuration is close to that obtained from gas-phase calculations. Different ratios of relative intensities of the proton triplet lines in the EPR spectra of isolated.NH2 radicals and.NH2−HF complexes were qualitatively explained by different heights of the barriers to rotation of the NH2 fragment in the Ar lattice. Kluwer Academic/Plenum Publishers, 2000 cryochemistry nationallicence EPR spectroscopy nationallicence fluorine nationallicence ammonia nationallicence radical-molecule complexes nationallicence radicals nationallicence Misochko E. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 14232, Chernogolovka, Russian Federation aut Gol'dshleger I. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 14232, Chernogolovka, Russian Federation aut Akimov A. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 14232, Chernogolovka, Russian Federation aut Russian Chemical Bulletin Kluwer Academic Publishers-Plenum Publishers 49/5(2000-05-01), 829-835 1066-5285 49:5<829 2000 49 11172 https://doi.org/10.1007/BF02494704 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF02494704 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Misochko E. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 14232, Chernogolovka, Russian Federation aut NATIONALLICENCE 700 1- Gol'dshleger I. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 14232, Chernogolovka, Russian Federation aut NATIONALLICENCE 700 1- Akimov A. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 14232, Chernogolovka, Russian Federation aut NATIONALLICENCE 773 0- Russian Chemical Bulletin Kluwer Academic Publishers-Plenum Publishers 49/5(2000-05-01), 829-835 1066-5285 49:5<829 2000 49 11172 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer