Vibrational spectroscopy of NO+(H2O)n

Evidence for the intracluster reaction NO+(H2O)n→ H3O+(H2O)n-2 (HONO) at n≥4

Jong-Ho Choi, Keith T. Kuwata, Bernd Michael Haas, Yibin Cao, Matthew S. Johnson, Mitchio Okumura

Research output: Contribution to journalArticle

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Abstract

Infrared spectra of mass-selected clusters NO+(H 2O)n for n=1 to 5 were recorded from 2700 to 3800 cm -1 by vibrational predissociation spectroscopy. Vibrational frequencies and intensities were also calculated for n=1 and 2 at the second-order Møller-Plesset (MP2) level, to aid in the interpretation of the spectra, and at the singles and doubles coupled cluster (CCSD) level energies of n=1 isomers were computed at the MP2 geometries. The smaller clusters (n=1 to 3) were complexes of H2O ligands bound to a nitrosonium ion NO+ core. They possessed perturbed H2O stretch bands and dissociated by loss of H2O. The H2O antisymmetric stretch was absent in n = 1 and gradually increased in intensity with n. In the n=4 clusters, we found evidence for the beginning of a second solvation shell as well as the onset of an intracluster reaction that formed HONO. These clusters exhibited additional weak, broad bands between 3200 and 3400 cm-1 and two new minor photodissociation channels, loss of HONO and loss of two H2O molecules. The reaction appeared to go to completion within the n=5 clusters. The primary dissociation channel was loss of HONO, and seven vibrational bands were observed. From an analysis of the spectrum, we concluded that the n=5 cluster rearranged to form H 3O+(H2O)3(HONO), i.e., an adduct of the reaction products.

Original languageEnglish
Pages (from-to)7153-7165
Number of pages13
JournalThe Journal of Chemical Physics
Volume100
Issue number10
Publication statusPublished - 1994 Dec 1
Externally publishedYes

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Vibrational spectroscopy
spectroscopy
Photodissociation
Solvation
Vibrational spectra
Reaction products
Isomers
Electron energy levels
Ligands
Infrared radiation
Molecules
Geometry
reaction products
photodissociation
adducts
solvation
infrared spectra
isomers
energy levels
dissociation

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Vibrational spectroscopy of NO+(H2O)n : Evidence for the intracluster reaction NO+(H2O)n→ H3O+(H2O)n-2 (HONO) at n≥4. / Choi, Jong-Ho; Kuwata, Keith T.; Haas, Bernd Michael; Cao, Yibin; Johnson, Matthew S.; Okumura, Mitchio.

In: The Journal of Chemical Physics, Vol. 100, No. 10, 01.12.1994, p. 7153-7165.

Research output: Contribution to journalArticle

Choi, Jong-Ho ; Kuwata, Keith T. ; Haas, Bernd Michael ; Cao, Yibin ; Johnson, Matthew S. ; Okumura, Mitchio. / Vibrational spectroscopy of NO+(H2O)n : Evidence for the intracluster reaction NO+(H2O)n→ H3O+(H2O)n-2 (HONO) at n≥4. In: The Journal of Chemical Physics. 1994 ; Vol. 100, No. 10. pp. 7153-7165.
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abstract = "Infrared spectra of mass-selected clusters NO+(H 2O)n for n=1 to 5 were recorded from 2700 to 3800 cm -1 by vibrational predissociation spectroscopy. Vibrational frequencies and intensities were also calculated for n=1 and 2 at the second-order M{\o}ller-Plesset (MP2) level, to aid in the interpretation of the spectra, and at the singles and doubles coupled cluster (CCSD) level energies of n=1 isomers were computed at the MP2 geometries. The smaller clusters (n=1 to 3) were complexes of H2O ligands bound to a nitrosonium ion NO+ core. They possessed perturbed H2O stretch bands and dissociated by loss of H2O. The H2O antisymmetric stretch was absent in n = 1 and gradually increased in intensity with n. In the n=4 clusters, we found evidence for the beginning of a second solvation shell as well as the onset of an intracluster reaction that formed HONO. These clusters exhibited additional weak, broad bands between 3200 and 3400 cm-1 and two new minor photodissociation channels, loss of HONO and loss of two H2O molecules. The reaction appeared to go to completion within the n=5 clusters. The primary dissociation channel was loss of HONO, and seven vibrational bands were observed. From an analysis of the spectrum, we concluded that the n=5 cluster rearranged to form H 3O+(H2O)3(HONO), i.e., an adduct of the reaction products.",
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