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Title: Ortho-para interconversion in cation-water complexes: The case of V+(H2O) and Nb+(H2O) clusters

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4984826· OSTI ID:1364008
 [1];  [2];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Georgia, Athens, GA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
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Vanadium and niobium cation-water complexes, V+(H2O) and Nb+(H2O), are produced by laser vaporization in a pulsed supersonic expansion, mass selected in a time-of-flight spectrometer, and studied with infrared photodissociation spectroscopy using rare gas atom (Ar, Ne) complex predissociation. The vibrational bands measured in the O–H stretching region contain K-type rotational sub-band structure, which provides insight into the structures of these complexes. However, rotational sub-bands do not exhibit the simple patterns seen previously for other metal ion-water complexes. We report the $$A$$ rotational constants are smaller than expected and the normal 1:3 intensity ratios for K = even:odd levels for independent ortho:para nuclear spin states are missing for some complexes. We relied on highly correlated internally contracted Multi-Reference Configuration Interaction (icMRCI) and Coupled Cluster [CCSD(T)] electronic structure calculations of those complexes with and without the rare gas atoms to investigate these anomalies. Rare gas atoms were found to bind via asymmetric motifs to the hydrated complexes undergoing large amplitude motions that vibrationally average to quasi-C2v symmetry with significant probability off the C2 axis, thus explaining the reduced $$A$$ values. Both vanadium and iobium cations exhibit unusually strong nuclear spin coupling to the hydrogen atoms of water, the values of which vary with their electronic state. This catalyzes ortho-para interconversion in some complexes and explains the rotational patterns. The rate of ortho-para relaxation in the equilibrated complexes must therefore be greater than the collisional cooling rate in the supersonic expansion (about 106 sec-1).

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
AC05-76RL01830; CHE-1464708; AC02-05CH11231
OSTI ID:
1364008
Alternate ID(s):
OSTI ID: 1366561
Report Number(s):
PNNL-SA-124984; KC0301050
Journal Information:
Journal of Chemical Physics, Vol. 146, Issue 22; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

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