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Bridging the Gap: Demonstrating the Connection Between Non-Valence Correlation-Bound Anions and Image Potential States Using a One-Electron Model

Mulvey, Devin M. (2024) Bridging the Gap: Demonstrating the Connection Between Non-Valence Correlation-Bound Anions and Image Potential States Using a One-Electron Model. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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Abstract

This work documents progress in developing a one-electron model Hamiltonian capable of simulating the non-valence correlation-bound (NVCB) anions of hexagonal polycylic aromatic hydrocarbons (PAHs) consisting of tens to thousands of atoms. The model potentials incorporate atomic electrostatic moments, coupled inducible atomic charges and dipoles, and atom-centered repulsive Gaussians parameterized on quantum mechanical data to describe the interaction between the excess electron and PAH. By comparing model results to reference all-electron dipole polarizabilities, electrostatic, and polarization potentials we validate that our model potential components capture the fundamental physics underlying the static and perturbation dependent properties of the PAHs. The electrostatic and polarization models reproduce the behavior expected of graphene when simulating the properties of large, finite molecules. By extracting the electron binding energies (EBEs) and single particle orbitals of the NVCB anions we validate model results against equation of motion (EOM) and random phase approximation (RPA) results. The model predicts a 1s-like ground state and a variety of excited state NVCB anions with wavefunctions resembling the hydrogenic 2s, 2p, 3p, 3d, 4f, and 5g orbitals for PAHs ranging in size from 54 to 5400 carbon atoms. We present results demonstrating that with increasing system size, the NVCB anions of these PAHs evolve into the image potential states (IPSs) of graphene. Despite polarization being the primary potential component binding these anions, we observe appreciable changes in the charge density of the excess electron due to electrostatics.

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Details

Item Type: University of Pittsburgh ETD
Status: Unpublished
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Mulvey, Devin M.dmm219@pitt.edudmm2190000-0001-5846-7162
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairJordan, Kenneth D.jordan@pitt.edu
Committee MemberCoalson, Robcoalson@pitt.edu
Committee MemberChong, Lillianltchong@pitt.edu
Committee MemberMisquitta, Alstona.j.misquitta@qmul.ac.uk
Date: 10 January 2024
Date Type: Publication
Defense Date: 28 November 2023
Approval Date: 10 January 2024
Submission Date: 7 December 2023
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Number of Pages: 199
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: Non-covlalent interaction Force field Carbon nanoflake Polycyclic Aromatic Hydrocarbon Graphene
Date Deposited: 10 Jan 2024 14:02
Last Modified: 10 Jan 2024 14:02
URI: http://d-scholarship.pitt.edu/id/eprint/45586

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