Show simple item record

dc.contributor.authorCaricato, Marco
dc.date.accessioned2016-07-15T18:52:08Z
dc.date.available2016-07-15T18:52:08Z
dc.date.issued2013
dc.identifier.citationA comparison between state-specific and linear-response formalisms for the calculation of vertical electronic transition energy in solution with the CCSD-PCM method, Caricato, Marco, The Journal of Chemical Physics, 139, 044116 (2013), DOI:http://dx.doi.org/10.1063/1.4816482en_US
dc.identifier.urihttp://hdl.handle.net/1808/21119
dc.description.abstractThe calculation of vertical electronic transition energies of molecular systems in solution with accurate quantum mechanical methods requires the use of approximate and yet reliable models to describe the effect of the solvent on the electronic structure of the solute. The polarizable continuum model (PCM) of solvation represents a computationally efficient way to describe this effect, especially when combined with coupled cluster (CC) methods. Two formalisms are available to compute transition energies within the PCM framework: State-Specific (SS) and Linear-Response (LR). The former provides a more complete account of the solute-solvent polarization in the excited states, while the latter is computationally very efficient (i.e., comparable to gas phase) and transition properties are well defined. In this work, I review the theory for the two formalisms within CC theory with a focus on their computational requirements, and present the first implementation of the LR-PCM formalism with the coupled cluster singles and doubles method (CCSD). Transition energies computed with LR- and SS-CCSD-PCM are presented, as well as a comparison between solvation models in the LR approach. The numerical results show that the two formalisms provide different absolute values of transition energy, but similar relative solvatochromic shifts (from nonpolar to polar solvents). The LR formalism may then be used to explore the solvent effect on multiple states and evaluate transition probabilities, while the SS formalism may be used to refine the description of specific states and for the exploration of excited state potential energy surfaces of solvated systems.en_US
dc.publisherAmerican Institute of Physicsen_US
dc.rightsCaricato, Marco, The Journal of Chemical Physics, AIP Advances, Vol. 139, 044116, (2013); used in accordance with the Creative Commons Attribution (CC BY) license.en_US
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.titleA comparison between state-specific and linear-response formalisms for the calculation of vertical electronic transition energy in solution with the CCSD-PCMen_US
dc.typeArticleen_US
kusw.kuauthorCaricato, Marco
kusw.kudepartmentChemistryen_US
dc.identifier.doi10.1063/1.4816482en_US
kusw.oaversionScholarly/refereed, publisher versionen_US
kusw.oapolicyThis item meets KU Open Access policy criteria.en_US
dc.rights.accessrightsopenAccess


Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record

Caricato, Marco, The Journal of Chemical Physics, AIP Advances, Vol. 139, 044116, (2013); used in accordance with the Creative Commons Attribution (CC BY) license.
Except where otherwise noted, this item's license is described as: Caricato, Marco, The Journal of Chemical Physics, AIP Advances, Vol. 139, 044116, (2013); used in accordance with the Creative Commons Attribution (CC BY) license.