Change search
ReferencesLink to record
Permanent link

Direct link
Ab initio study of excited state electronic circular dichroism. Two prototype cases: Methyl oxirane and R-(+)-1,1 '-bi(2-naphthol)
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0002-9123-8174
2011 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 134, no 24Article in journal (Refereed) Published
Abstract [en]

A computational approach to the calculation of excited state electronic circular dichroism (ESECD) spectra of chiral molecules is discussed. Frequency dependent quadratic response theory is employed to compute the rotatory strength for transitions between excited electronic states, by employing both a magnetic gauge dependent and a (velocity-based) magnetic gauge independent approach. Application is made to the lowest excited states of two prototypical chiral molecules, propylene oxide, also known as 1,2-epoxypropane or methyl oxirane, and R-(+)-1,1'-bi(2-naphthol), or BINOL. The dependence of the rotatory strength for transitions between the lowest three excited states of methyl oxirane upon the quality and extension of the basis set is analyzed, by employing a hierarchy of correlation consistent basis sets. Once established that basis sets of at least triple zeta quality, and at least doubly augmented, are sufficient to ensure sufficiently converged results, at least at the Hartree-Fock self-consistent field (HF-SCF) level, the rotatory strengths for all transitions between the lowest excited electronic states of methyl oxirane are computed and analyzed, employing HF-SCF, and density functional theory (DFT) electronic structure models. For DFT, both the popular B3LYP and its recently highly successful CAM-B3LYP extension are exploited. The strong dependence of the spectra upon electron correlation is highlighted. A HF-SCF and DFT study is carried out also for BINOL, a system where excited states show the typical pairing structure arising from the interaction of the two monomeric moieties, and whose conformational changes following photoexcitation were studied recently with via time-resolved CD.

Place, publisher, year, edition, pages
2011. Vol. 134, no 24
Keyword [en]
ab initio calculations, circular dichroism, density functional theory, electron correlations, excited states, HF calculations, molecular configurations, molecular electronic states, molecule-photon collisions, optical rotation
National Category
Physical Sciences
URN: urn:nbn:se:kth:diva-36887DOI: 10.1063/1.3602219ISI: 000292331900012OAI: diva2:431503
QC 20110720Available from: 2011-07-20 Created: 2011-07-18 Last updated: 2011-07-20Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text

Search in DiVA

By author/editor
Vahtras, Olav
By organisation
Theoretical Chemistry and Biology
In the same journal
Journal of Chemical Physics
Physical Sciences

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 10 hits
ReferencesLink to record
Permanent link

Direct link