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Titolo:
Infrared spectrum of the H3N-HI complex in solid Ne, Ar, Ne/Ar, Kr, and N-2. Comparisons of matrix effects on hydrogen-bonded complexes
Autore:
Andrews, L; Wang, XF;
Indirizzi:
Univ Virginia, Dept Chem, Charlottesville, VA 22904 USA Univ Virginia Charlottesville VA USA 22904 Charlottesville, VA 22904 USA
Titolo Testata:
JOURNAL OF PHYSICAL CHEMISTRY A
fascicolo: 32, volume: 105, anno: 2001,
pagine: 7541 - 7550
SICI:
1089-5639(20010816)105:32<7541:ISOTHC>2.0.ZU;2-2
Fonte:
ISI
Lingua:
ENG
Soggetto:
ISOLATION VIBRATIONAL SPECTROSCOPY; PROTON-TRANSFER; HALIDE-COMPLEXES; INERT MATRICES; ARGON MATRICES; GAS-PHASE; AB-INITIO; ION-PAIR; AMMONIA; VAPOR;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
52
Recensione:
Indirizzi per estratti:
Indirizzo: Andrews, L Univ Virginia, Dept Chem, Mccormick Rd, Charlottesville, VA 22904 USA Univ Virginia Mccormick Rd Charlottesville VA USA 22904 904 USA
Citazione:
L. Andrews e X.F. Wang, "Infrared spectrum of the H3N-HI complex in solid Ne, Ar, Ne/Ar, Kr, and N-2. Comparisons of matrix effects on hydrogen-bonded complexes", J PHYS CH A, 105(32), 2001, pp. 7541-7550

Abstract

Ammonia and hydrogen iodide vapors from the thermal decomposition of NH4I were codeposited with excess neon at 5 K to form the H3N-HI complex. New 630, 1192, and 3435 cm(-1) infrared absorptions are assigned to the antisymmetric N-H-I stretching, symmetric NH3 bending, and antisymmetric NH3 stretching modes of the 1:1 complex. Vibrational assignments are supported by (NH3)-N-15, ND4I, and mixed H/D isotopic substitution. Complementary experiments were done with argon, neon/argon mixtures, krypton, and nitrogen to investigate the 1:1 complex in a range of matrix environments and to compare with previous work using the reagent gases. The above modes are shifted to 592, 1259, and 3400 cm(-1) in solid argon owing to an increased interaction with the more polarizable argon matrix atoms. Neon and 2% argon mixtures gaveintermediate absorptions, which evolved to the pure argon values on annealing to allow diffusion. The strong nitrogen matrix infrared absorption at 1955 cm(-1) shifts approximately 4 cm(-1) with N-15-substitution, which suggests an N-H stretching mode and substantial proton transfer toward a more ionic complex in the nitrogen host. These and earlier matrix isolation experiments show that the matrix environment markedly affects the hydrogen bonding interaction and the degree of proton transfer in this polar H3N-HI hydrogen-bonded complex.

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Documento generato il 25/11/20 alle ore 00:53:33