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Cui, Jun (2007) VIBRATIONAL SPECTRA AND n-BODY DECOMPOSITION ANALYSESOF WATER CLUSTERS. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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The hydrated proton lies at the heart of several key charge transport processes in chemistry and biology, and yet the molecular level description of proton accommodation remains elusive. Both H3O+ (so called Eigen) and (H2O···H···OH2)+ (so called Zundel) have long been thought to play essential roles in the proton transfer process. We characterize the hydrated proton with a "bottom up" approach to monitor the spectral evolution of the proton accommodation motif as water molecules are sequentially added to the H3O+ ion. It is found that a highly symmetrical structure is necessary to observe the Eigen ion. Small asymmetries in the hydration structure around the H3O+ core result in preferential localization of the excess charge on one or two of the hydrogen atoms. This extreme response to symmetry breaking readily explains the lack of a crisp spectral signature of the hydrated proton in the bulk. Density functional theory is used to study the relative stability of various isomers of (H2O)n · H+, n = 4-12, allowing for the influence of vibrational zero point energy and finite temperature effects. Comparison of experimental spectra with and without Ar tagging shows that the inclusion of Ar atoms has little effect on the frequencies.Two low-energy minima of (H2O)21 with very different H-bonding arrangements have been investigated with the B3LYP density functional and RIMP2 methods, as well as with the TIP4P, Dang-Chang, AMOEBA, and TTM2-F force fields. Insight into the role of many-body polarization for establishing the relative stability of the two isomers is provided by an n-body decomposition of the energies calculated using the various theoretical methods.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairJordan, Kenneth
Committee MemberMadura, Jeffry
Committee MemberGrabowski, Joseph Jjoeg@pitt.eduJOEG
Committee MemberSiska, Peter Epes@pitt.eduPES
Date: 20 June 2007
Date Type: Completion
Defense Date: 24 April 2007
Approval Date: 20 June 2007
Submission Date: 26 April 2007
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Institution: University of Pittsburgh
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Degree: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: cluster; decomposition; n-body; spectra; vibrational; water
Other ID:, etd-04262007-140823
Date Deposited: 10 Nov 2011 19:42
Last Modified: 15 Nov 2016 13:42


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