First principles simulations of vibrational spectra of aqueous systems /

First principles simulations of vibrational spectra of aqueous systems /

Saved in:
Bibliographic Details
Author / Creator:Wan, Quan, author.
Imprint:2015.
Ann Arbor : ProQuest Dissertations & Theses, 2015
Description:1 electronic resource (139 pages)
Language:English
Format: E-Resource Dissertations
Local Note:School code: 0330
URL for this record:http://pi.lib.uchicago.edu/1001/cat/bib/10773288
Hidden Bibliographic Details
Other authors / contributors:University of Chicago. degree granting institution.
ISBN:9781339080857
Notes:Advisors: Giulia Galli Committee members: Giulia Galli; Andrei Tokmakoff; Juan de Pablo.
Dissertation Abstracts International, Volume: 77-02(E), Section: B.
English
Summary:Vibrational spectroscopy is an ideal tool to probe the complex structure of ice, water and other aqueous systems. However, the interpretation of experimental spectra is usually not straightforward, due to complex spectral features associated with different bonding configurations present in these systems. Therefore, accurate theoretical predictions are required to assign spectral signatures to specific structural properties and hence to fully exploit the potential of vibrational spectroscopies. My dissertation focused on the development and applications of first-principles electronic structure methods for the simulation of vibrational spectra of water and aqueous systems, as well as of their basic electronic properties.
In particular, I focused on the calculation of response properties of aqueous systems in the presence of external electric fields, including the computation of dipole and quadrupole moments and polarizabilities, which were then used to simulate vibrational spectra, e.g. Raman and sum frequency generation (SFG) spectra. I developed linear response and finite field methods based on electronic structure calculations within density functional theory (DFT), which were applied to accurate and efficient evaluations of the electric field response, and coupled to large-scale first-principles electronic structure and molecular dynamics (MD) simulations. Our implementation enabled on-the-fly calculations of polarizabilities in first-principles MD (FPMD) simulations, which are necessary to compute vibrational spectra using time correlation functions (TCF) formulations. In addition, in this dissertation I provide the first ab initio implementation of SFG calculations, inclusive of quadrupole contributions as well as of electric field gradients at the interface.
I present the first calculation of the Raman spectra of liquid water using FPMD simulations. Interesting signatures were found in the low frequency region of the spectra, indicating intermolecular charge fluctuations that accompany hydrogen bond stretching vibrations. Furthermore I applied the newly developed method for the calculation of SFG spectra, a surface specific spectroscopic probe, to the investigation of the ice Ih basal surfaces. Note that all the methods developed here, although only applied to aqueous systems, are of general applicability to semiconductors and insulators.
Finally I present investigations of the vibrational and electronic properties of aqueous sulfuric acid systems, including sulfate-water clusters and sulfuric acid solutions. Our results on the energy alignment between sulfate and water states bear important implications on the relative reactivities of ions and water in electrochemical environment used in water splitting reactions.

MARC

LEADER 00000ntm a22000003i 4500
001 10773288
003 ICU
005 20230627195705.7
007 cr un|---|||||
008 151222s2015 miu||||||m |||| ||eng d
020 |a 9781339080857 
035 |a (MiAaPQD)AAI3724564 
035 |a AAI3724564 
040 |a MiAaPQD  |b eng  |c MiAaPQD  |e rda 
100 1 |a Wan, Quan,  |e author. 
245 1 0 |a First principles simulations of vibrational spectra of aqueous systems /  |c Wan, Quan. 
260 |c 2015. 
264 1 |a Ann Arbor :  |b ProQuest Dissertations & Theses,  |c 2015 
300 |a 1 electronic resource (139 pages) 
336 |a text  |b txt  |2 rdacontent 
337 |a computer  |b c  |2 rdamedia 
338 |a online resource  |b cr  |2 rdacarrier 
500 |a Advisors: Giulia Galli Committee members: Giulia Galli; Andrei Tokmakoff; Juan de Pablo. 
502 |b Ph.D.  |c The University of Chicago, Institute for Molecular Engineering  |d 2015. 
510 4 |a Dissertation Abstracts International,  |c Volume: 77-02(E), Section: B. 
520 |a Vibrational spectroscopy is an ideal tool to probe the complex structure of ice, water and other aqueous systems. However, the interpretation of experimental spectra is usually not straightforward, due to complex spectral features associated with different bonding configurations present in these systems. Therefore, accurate theoretical predictions are required to assign spectral signatures to specific structural properties and hence to fully exploit the potential of vibrational spectroscopies. My dissertation focused on the development and applications of first-principles electronic structure methods for the simulation of vibrational spectra of water and aqueous systems, as well as of their basic electronic properties. 
520 |a In particular, I focused on the calculation of response properties of aqueous systems in the presence of external electric fields, including the computation of dipole and quadrupole moments and polarizabilities, which were then used to simulate vibrational spectra, e.g. Raman and sum frequency generation (SFG) spectra. I developed linear response and finite field methods based on electronic structure calculations within density functional theory (DFT), which were applied to accurate and efficient evaluations of the electric field response, and coupled to large-scale first-principles electronic structure and molecular dynamics (MD) simulations. Our implementation enabled on-the-fly calculations of polarizabilities in first-principles MD (FPMD) simulations, which are necessary to compute vibrational spectra using time correlation functions (TCF) formulations. In addition, in this dissertation I provide the first ab initio implementation of SFG calculations, inclusive of quadrupole contributions as well as of electric field gradients at the interface. 
520 |a I present the first calculation of the Raman spectra of liquid water using FPMD simulations. Interesting signatures were found in the low frequency region of the spectra, indicating intermolecular charge fluctuations that accompany hydrogen bond stretching vibrations. Furthermore I applied the newly developed method for the calculation of SFG spectra, a surface specific spectroscopic probe, to the investigation of the ice Ih basal surfaces. Note that all the methods developed here, although only applied to aqueous systems, are of general applicability to semiconductors and insulators. 
520 |a Finally I present investigations of the vibrational and electronic properties of aqueous sulfuric acid systems, including sulfate-water clusters and sulfuric acid solutions. Our results on the energy alignment between sulfate and water states bear important implications on the relative reactivities of ions and water in electrochemical environment used in water splitting reactions. 
546 |a English 
590 |a School code: 0330 
690 |a Chemistry. 
690 |a Physical chemistry. 
710 2 |a University of Chicago.  |e degree granting institution. 
720 1 |a Giulia Galli  |e degree supervisor. 
856 4 0 |u http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqm&rft_dat=xri:pqdiss:3724564  |y ProQuest 
929 |a eresource 
999 f f |i 024e5198-d2d6-5672-85c4-0bfe1c6f909e  |s 1b266e12-878b-576c-9337-6214e6d60541 
928 |t Library of Congress classification  |l Online  |c UC-FullText  |u http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqm&rft_dat=xri:pqdiss:3724564  |z ProQuest  |i 9079515 

Similar Items