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 language | English |
|---|---|
| Pages (from-to) | 7153-7165 |
| Number of pages | 13 |
| Journal | The Journal of Chemical Physics |
| Volume | 100 |
| Issue number | 10 |
| Publication status | Published - 1994 Dec 1 |
| Externally published | Yes |
Fingerprint
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 journal › Article
}
TY - JOUR
T1 - Vibrational spectroscopy of NO+(H2O)n
T2 - Evidence for the intracluster reaction NO+(H2O)n→ H3O+(H2O)n-2 (HONO) at n≥4
AU - Choi, Jong-Ho
AU - Kuwata, Keith T.
AU - Haas, Bernd Michael
AU - Cao, Yibin
AU - Johnson, Matthew S.
AU - Okumura, Mitchio
PY - 1994/12/1
Y1 - 1994/12/1
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=36449000284&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=36449000284&partnerID=8YFLogxK
M3 - Article
VL - 100
SP - 7153
EP - 7165
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 10
ER -