Electronic circular dichroism spectroscopy of 1-(R)-phenylethanol: the “sector rule” revisited and an exploration of solvent effects

2.50
Hdl Handle:
http://hdl.handle.net/10547/294527
Title:
Electronic circular dichroism spectroscopy of 1-(R)-phenylethanol: the “sector rule” revisited and an exploration of solvent effects
Authors:
Macleod, Neil A.; Butz, Patrick; Simons, John P.; Grant, Guy H.; Baker, Christopher M.; Tranter, George E.
Abstract:
The sensitivity of the electronic circular dichroism (ECD) of a chiral molecule to structural and environmental changes has been investigated using 1-(R)-phenylethanol (1-PE) as the benchmark solute and cyclohexane and water as the trial solvents. Rotatory strengths associated with the π → π* (1Lb) electronic transition have been calculated ab initio for: (a) isolated 1-PE, as a function of the dihedral angles within its chiral side chain and between the side chain and the aromatic ring: these confirm the validity of the empirical “sector rule” but with the signs reversed; (b) the singly and doubly hydrated clusters of 1-PE, isolated in the gas phase; (c) 1-PE and its singly and doubly hydrated clusters embedded in a polarizable dielectric continuum; and (d) 1-PE in an aqueous solution interacting with the local hydration shell and with the polarizable dielectric continuum, using averaged solute structures computed from the fluctuating solute and solvent configurations generated via molecular dynamics simulations.
Citation:
Macleod, N.A., Butz, P., Simons, J.P., Grant, G.H., Baker, C.M. and Tranter, G.E. (2004) ' Electronic Circular dichroism spectroscopy of 1-(R)-phenylethanol: the “Sector Rule” revisited and an exploration of solvent effects', Israel Journal of Chemistry, 44 (1-3),pp.27-36.
Publisher:
Wiley
Journal:
Israel Journal of Chemistry
Issue Date:
2004
URI:
http://hdl.handle.net/10547/294527
DOI:
10.1560/LM77-UMAV-80EF-VYWC
Additional Links:
http://doi.wiley.com/10.1560/LM77-UMAV-80EF-VYWC
Type:
Article
Language:
en
ISSN:
0021-2148; 1869-5868
Appears in Collections:
Cell and Cryobiology Research Group

Full metadata record

DC FieldValue Language
dc.contributor.authorMacleod, Neil A.en_GB
dc.contributor.authorButz, Patricken_GB
dc.contributor.authorSimons, John P.en_GB
dc.contributor.authorGrant, Guy H.en_GB
dc.contributor.authorBaker, Christopher M.en_GB
dc.contributor.authorTranter, George E.en_GB
dc.date.accessioned2013-06-25T15:04:28Z-
dc.date.available2013-06-25T15:04:28Z-
dc.date.issued2004-
dc.identifier.citationMacleod, N.A., Butz, P., Simons, J.P., Grant, G.H., Baker, C.M. and Tranter, G.E. (2004) ' Electronic Circular dichroism spectroscopy of 1-(R)-phenylethanol: the “Sector Rule” revisited and an exploration of solvent effects', Israel Journal of Chemistry, 44 (1-3),pp.27-36.en_GB
dc.identifier.issn0021-2148-
dc.identifier.issn1869-5868-
dc.identifier.doi10.1560/LM77-UMAV-80EF-VYWC-
dc.identifier.urihttp://hdl.handle.net/10547/294527-
dc.description.abstractThe sensitivity of the electronic circular dichroism (ECD) of a chiral molecule to structural and environmental changes has been investigated using 1-(R)-phenylethanol (1-PE) as the benchmark solute and cyclohexane and water as the trial solvents. Rotatory strengths associated with the π → π* (1Lb) electronic transition have been calculated ab initio for: (a) isolated 1-PE, as a function of the dihedral angles within its chiral side chain and between the side chain and the aromatic ring: these confirm the validity of the empirical “sector rule” but with the signs reversed; (b) the singly and doubly hydrated clusters of 1-PE, isolated in the gas phase; (c) 1-PE and its singly and doubly hydrated clusters embedded in a polarizable dielectric continuum; and (d) 1-PE in an aqueous solution interacting with the local hydration shell and with the polarizable dielectric continuum, using averaged solute structures computed from the fluctuating solute and solvent configurations generated via molecular dynamics simulations.en_GB
dc.language.isoenen
dc.publisherWileyen_GB
dc.relation.urlhttp://doi.wiley.com/10.1560/LM77-UMAV-80EF-VYWCen_GB
dc.rightsArchived with thanks to Israel Journal of Chemistryen_GB
dc.titleElectronic circular dichroism spectroscopy of 1-(R)-phenylethanol: the “sector rule” revisited and an exploration of solvent effectsen
dc.typeArticleen
dc.identifier.journalIsrael Journal of Chemistryen_GB
All Items in UOBREP are protected by copyright, with all rights reserved, unless otherwise indicated.