Date of Award
8-23-2010
Document Type
Thesis
Degree Name
Chemistry, MS
First Advisor
Hideya Koizumi
Committee Members
Hashim Ali; Hideya Koizumi; William Burns
Call Number
LD 251 .A566t 2010 A72
Abstract
The IEFPCM conformational study of 12c4 in aqueous phase with B3LYP/6-31+G* and metal ion complex, M+(12c4), M= Li, Na and K withB3LYP, B3P86, B3PW91 and mPW3PBE using 6-31+G* basis sets are performed. Our result shows that the ground state conformer of 12c4 in gas phase, 1(S4) has population of no more than 2% in aqueous solution. The conformer 11(C1) structure was diagnosed to be the most populated conformer while B3LYP method predicts the conformer 6(Ci) has the lowest energy. The metal ion (Li+, Na+, K+) selectivity of 12c4 in aqueous phase is determined by the isodesmic reaction. The ensemble averaged enthalpy of association (Hassoc) and free energy of association (Gassoc) are determined by IEFPCM with B3LYP/6-31+G* and B3P86/6-31+G*. The Hassoc and Gassoc were calculated using a variety of functionals (B3LYP, B3P86, B3PW91, mPW3PBE, PBE1PBE, and CAM-B3LYP) and basis sets(6-31+G* and 6-311+G*); and all results indicated that Li+ ion binds stronger than Na+ or K+ in aqueous phase. The ensemble averaged <<Hassoc>> and <<Gassoc>> over the average of the all DFT/6-311+G* methods studied here are -50.7 and -9.8, -49.0 and -7.4, and -45.4 and -3.6 kJ/mol for M= Li, Na, and K, respectively.
Rights Management
This work is licensed under a Creative Commons Attribution 4.0 International License.
Recommended Citation
Arora, Tanika, "New C1 Geometries for Free 12-Crown-4 in Aqueous Solution and the Absolute Selectivity of 12-Crown-4 on Alkali Metal Ions in Aqueous Solution: A Theoretical Study" (2010). Student Theses and Dissertations. 951.
https://arch.astate.edu/all-etd/951
