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dc.contributor.authorMach, Taylor Josephen_US
dc.date.accessioned2015-12-09T07:00:23Z
dc.date.available2015-12-09T07:00:23Z
dc.date.issued2014-06-16en_US
dc.identifier.othervt_gsexam:2940en_US
dc.identifier.urihttp://hdl.handle.net/10919/64301
dc.description.abstractAccurate theoretical predictions of optical rotation are of substantial utility to the chemical community enabling the determination of absolute configuration without the need for poten- tially lengthy total synthesis. The requirements for robust calculation of gas-phase optical rotation are well understood, but too expensive for routine use. In an effort to reduce this cost we have examined the performance of the LPol and ORP basis sets, created for use in density functional theory calculations of optical rotation, finding that at the coupled cluster level of theory they perform the same or better than comparably sized general basis sets that are often used. We have also examined the performance of a perturbational approach to inclusion of explicit solvent molecules in an effort to extend the calculation of response properties from the gas phase to the condensed phase. This N-body approach performs admirably for interaction energies and even dipole moments but breaks down for optical rotation, exhibiting large basis set superposition errors and requiring higher-order terms in the expansion to provide reasonable accuracy. In addition, we have begun the process of implementing a gauge invariant version of coupled cluster response properties to address the fundamentally unphysical lack of gauge invariance in coupled cluster optical rotations. Correcting this problem, which arises from the non- variational nature of the coupled cluster wavefunction, involves reformulating the response amplitude and function expressions and solving for all necessary amplitudes simultaneously.en_US
dc.format.mediumETDen_US
dc.publisherVirginia Techen_US
dc.rightsThis Item is protected by copyright and/or related rights. Some uses of this Item may be deemed fair and permitted by law even without permission from the rights holder(s), or the rights holder(s) may have licensed the work for use under certain conditions. For other uses you need to obtain permission from the rights holder(s).en_US
dc.subjectOptical Rotationen_US
dc.subjectCoupled Clusteren_US
dc.subjectGauge Invarianceen_US
dc.subjectN-Bodyen_US
dc.titleAccurate Prediction of Chiroptical Propertiesen_US
dc.typeDissertationen_US
dc.contributor.departmentChemistryen_US
dc.description.degreePh. D.en_US
thesis.degree.namePh. D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen_US
thesis.degree.disciplineChemistryen_US
dc.contributor.committeechairCrawford, Daniel T.en_US
dc.contributor.committeememberDeck, Paul A.en_US
dc.contributor.committeememberTroya, Diegoen_US
dc.contributor.committeememberValeyev, Eduard Faritovichen_US


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