Infrared depletion spectroscopy of the doubly hydrogen-bonded aniline–(tetrahydrofuran)2 complex produced in supersonic jet |
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Authors: | Pradyot K. Chowdhury |
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Affiliation: | National Institute for Advanced Interdisciplinary Research, 1-1-4 Higashi, Tsukuba, Ibaraki 305, Japan |
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Abstract: | The vibrational frequencies of the N–H stretching modes of aniline after forming a strong doubly H-bonded complex with tetrahydrofuran (THF) are measured with infrared depletion spectroscopy that uses cluster-size-selective resonance-enhanced multiphoton ionization (REMPI) time-of-flight mass spectrometry. Two strong infrared absorption features observed at 3355 and 3488 cm−1 are assigned to the symmetric and antisymmetric N–H stretching vibrations of the 1:2 aniline–THF complex, respectively. The red-shifts of the N–H stretching vibrations of aniline agree with the ab initio calculated (MP2/6-31G**) aniline-(THF)2 structure in which both aniline N–H bonds interact with the oxygen atom of THF through two hydrogen bonds. The calculated binding energy is found to be 29.6 kJ mol−1 after corrections for basis set superposition error (BSSE) and zero-point energy. The calculated structure revealed that the angle between the N–H bonds in the NH2 group increased to 112.5° in the aniline–(THF)2 complex from that of 109.8° in the aniline. The electronic 0–0 band origin for the S1 ← S0 transition is observed at 32,900 cm−1 in the aniline–(THF)2 complex, giving a red-shift of 1129 cm−1 from that of the aniline molecule. |
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Keywords: | Hydrogen-bonded complex REMPI Infrared depletion spectroscopy Ab initio calculation |
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