Electronic and Vibrational Spectroscopy of Ni+(H2O)

The 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 ~3...

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Main Author: Daluz, Jennifer S.
Format: Others
Published: ScholarWorks@UMass Amherst 2011
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Online Access:https://scholarworks.umass.edu/theses/594
https://scholarworks.umass.edu/cgi/viewcontent.cgi?article=1717&context=theses
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spelling ndltd-UMASS-oai-scholarworks.umass.edu-theses-17172020-12-02T14:44:14Z Electronic and Vibrational Spectroscopy of Ni+(H2O) Daluz, Jennifer S. The 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. 2011-01-01T08:00:00Z text application/pdf https://scholarworks.umass.edu/theses/594 https://scholarworks.umass.edu/cgi/viewcontent.cgi?article=1717&context=theses Masters Theses 1911 - February 2014 ScholarWorks@UMass Amherst Electronic and Vibrational Spectroscopy of Ni+(H2O) Physical Chemistry
collection NDLTD
format Others
sources NDLTD
topic Electronic and Vibrational Spectroscopy of Ni+(H2O)
Physical Chemistry
spellingShingle Electronic and Vibrational Spectroscopy of Ni+(H2O)
Physical Chemistry
Daluz, Jennifer S.
Electronic and Vibrational Spectroscopy of Ni+(H2O)
description The 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.
author Daluz, Jennifer S.
author_facet Daluz, Jennifer S.
author_sort Daluz, Jennifer S.
title Electronic and Vibrational Spectroscopy of Ni+(H2O)
title_short Electronic and Vibrational Spectroscopy of Ni+(H2O)
title_full Electronic and Vibrational Spectroscopy of Ni+(H2O)
title_fullStr Electronic and Vibrational Spectroscopy of Ni+(H2O)
title_full_unstemmed Electronic and Vibrational Spectroscopy of Ni+(H2O)
title_sort electronic and vibrational spectroscopy of ni+(h2o)
publisher ScholarWorks@UMass Amherst
publishDate 2011
url https://scholarworks.umass.edu/theses/594
https://scholarworks.umass.edu/cgi/viewcontent.cgi?article=1717&context=theses
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