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Electronic and Vibrational Spectroscopy of Ni+(H2O)

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dc.contributor.advisorRicardo B. Metz
dc.contributor.authorDaluz, Jennifer S.
dc.contributor.departmentUniversity of Massachusetts Amherst
dc.contributor.departmentChemistry
dc.date2023-09-23T03:40:50.000
dc.date.accessioned2024-04-26T21:12:20Z
dc.date.available2011-04-15T00:00:00Z
dc.date.issued2011-01-01
dc.date.submittedMay
dc.description.abstractThe electronic and vibrational spectra of Ni+(H2O) were measured using photofragment spectroscopy. In the electronic spectrum, photodissociation is observed at photon energies above 16875 cm-1. The only fragment observed is Ni+. The electronic spectrum consists of well-resolved peaks spaced by ~340 cm-1, due to a vibrational progression in the excited electronic state. These peaks have complex sub-structure, consisting of a triplet, spaced by ~30 cm-1. The sub-structure is due to rotational structure in a perpendicular transition of a prolate top molecule. In addition to this major progression, there is a series of less intense, single peaks spaced by ~340 cm-1. These may be due to a vibrational progression in a second electronic state, this time due to a parallel transition. The O-H stretching vibrations of Ni+(H2O) were measured using vibrationally mediated photodissociation (VMP) in a depletion experiment, only monitoring transitions from K’’=1. This revealed a O-H symmetric stretch at 3629 cm-1 and antisymmetric O-H stretch at 3692 cm-1. Several electronic structure calculations complement the experiments using the BHandHLYP hybrid density functional and the 6-311++G(3dp, f) basis set. At this level of theory, Ni+(H2O) is predicted to have C2v symmetry and 2A1 ground state. The Ni-O bond length is 1.95, the O-H bond lengths are .955 and the H-O-H angle is 108.2˚ The molecule is a near-prolate top, with rotational constants A=13.98 cm-1, B=0.297 cm-1 and C=0.296 cm-1 . Analysis of the electronic and vibrational spectra reveals that binding to Ni+ removes electron density from the oxygen lone pairs, increasing the H-O-H bond angle from its value in bare H2O. The electronic and vibrational spectra corresponds to 4s ¬3d transistion in Ni+. As a result of electronic excitation, the Ni-O bond stretches by .20 Å, and the H-O-H bond angle is reduced.
dc.description.degreeMaster of Science (M.S.)
dc.identifier.doihttps://doi.org/10.7275/1942620
dc.identifier.urihttps://hdl.handle.net/20.500.14394/47494
dc.relation.urlhttps://scholarworks.umass.edu/cgi/viewcontent.cgi?article=1717&context=theses&unstamped=1
dc.source.statuspublished
dc.subjectElectronic and Vibrational Spectroscopy of Ni+(H2O)
dc.subjectPhysical Chemistry
dc.titleElectronic and Vibrational Spectroscopy of Ni+(H2O)
dc.typeopen
dc.typearticle
dc.typethesis
digcom.contributor.authorisAuthorOfPublication|email:jdaluz@chem.umass.edu|institution:University of Massachusetts Amherst|Daluz, Jennifer S.
digcom.date.embargo2011-04-15T00:00:00-07:00
digcom.identifiertheses/594
digcom.identifier.contextkey1942620
digcom.identifier.submissionpaththeses/594
dspace.entity.typePublication
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