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Theoretical Approaches for Studying Non-Valence Correlation-Bound and Correlation-Assisted Anion States of Molecules and Molecular Clusters

Kairalapova, Arailym (2020) Theoretical Approaches for Studying Non-Valence Correlation-Bound and Correlation-Assisted Anion States of Molecules and Molecular Clusters. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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Non-valence correlation-bound and correlation-assisted anion states of molecules and molecular clusters have been characterized using various electronic structure methods. In these species long-range dispersion type correlation interactions are responsible for binding of the excess electron in a spatially diffuse orbital. Therefore, the Hartree-Fock method and methods that depend on the Hartree-Fock wave function being a suitable reference fail to bind such anions or greatly underestimate the electron binding energy. The main approach used in the present studies is the equation of motion coupled-cluster method. Additional methods may also accurately describe these non-valence anions provided adequate orbital relaxation in response to long-range dispersion-like correlation effects is included. Non-valence correlation- bound anion states of a model (H2O)4 cluster, the bent CO2, and tetracyanoethylene are characterized.
In addition to bound non-valence anions, some species may possess temporary anion states that lie energetically above the ground state of the neutral molecule and, thus, are subject to electron autodetachment. These temporary anion shape resonances are trapped by a potential barrier and are characterized by a complex energy. The temporary anion shape resonances of the model (H2O)4 cluster and rhombic (NaCl)2 are described. In case of (H2O)4 cluster, the shape resonance corresponds to an asymmetric combination of the dipole-bound anion states of the subunit dimers. The resonance energy is determined as a function of the distance between the dimers of the (H2O)4 cluster. The temporary anion shape resonance of (NaCl)2 corresponds to an antibonding combination of the hybridized orbitals associated with the two Na atoms. The resonance energy is determined as a function of distortion along the totally symmetric normal coordinate.
Finally, the molecular virial theorem is studied for a H atom interacting with a uniform electric field or with a point charge. Analytical expressions of the contributions to changes in average kinetic and potential energies due to these interactions are obtained by use of Dalgarno-Lewis perturbation theory.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Kairalapova, Arailymark118@pitt.eduark118
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairJordan,
Committee MemberLiu,
Committee MemberGarrett-Roe,
Committee MemberYaron,
Date: 16 September 2020
Date Type: Publication
Defense Date: 24 July 2020
Approval Date: 16 September 2020
Submission Date: 5 August 2020
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Number of Pages: 113
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-valence anions, Non-valence anions
Date Deposited: 16 Sep 2020 14:11
Last Modified: 16 Sep 2020 14:11

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