Microwave Spectra of the Deuterium Isotopologues of cis-Hexatriene and a Semiexperimental Equilibrium Structure

Title:
Microwave Spectra of the Deuterium Isotopologues of cis-Hexatriene and a Semiexperimental Equilibrium Structure
Authors:
Craig, Norman C.; Chen, Yihui; Fuson, Hannah A.; Tian, Hengfeng; van Besien, Herman; Conrad, Andrew R.; Tubergen, Michael J.; Rudolph, Heinz Dieter; Demaison, Jean
Abstract:
Microwave transitions and ground state rotational constants are reported for five newly synthesized deuterium isotopologues of cis-1,3,5-hexatriene (cHTE). These rotational constants along with those of the parent and the three 13C species are used with vibration–rotation constants calculated from an MP2/cc-pVTZ model to derive an equilibrium structure. That structure is improved by the mixed estimation method. In this method, internal coordinates from good-quality quantum chemical calculations (with appropriate uncertainties) are fit simultaneously with moments of inertia of the full set of isotopologues. The new structure of cHTE is confirmed to be planar and is stabilized by an interaction between the hydrogen atoms H2 and H5, which form a bond and participate in a six-membered ring. cHTE shows larger structural effects of π-electron delocalization than does butadiene with the effects being magnified in the center of the molecule. Thus, strong structural evidence now exists for an increase in π-electron delocalization as the polyene chain lengthens.
Citation:
Craig, N.C., Y. Chen, H.A. Fuson, H. Tian, H. van Besien, A.R. Conrad, M.J. Tubergen, H.D. Rudolph, and J. Demaison. 2013. "Microwave Spectra of the Deuterium Isotopologues of cis-Hexatriene and a Semiexperimental Equilibrium Structure." Journal of Physical Chemistry A 117(39): 9391-9400.
Publisher:
American Chemical Society
DATE ISSUED:
2013
Department:
Chemistry
Type:
Article
PUBLISHED VERSION:
10.1021/jp311035c
PERMANENT LINK:
http://hdl.handle.net/11282/334054

Full metadata record

DC FieldValue Language
dc.contributor.authorCraig, Norman C.en
dc.contributor.authorChen, Yihuien
dc.contributor.authorFuson, Hannah A.en
dc.contributor.authorTian, Hengfengen
dc.contributor.authorvan Besien, Hermanen
dc.contributor.authorConrad, Andrew R.en
dc.contributor.authorTubergen, Michael J.en
dc.contributor.authorRudolph, Heinz Dieteren
dc.contributor.authorDemaison, Jeanen
dc.date.accessioned2014-11-10T14:13:08Z-
dc.date.available2014-11-10T14:13:08Z-
dc.date.issued2013en
dc.identifier.citationCraig, N.C., Y. Chen, H.A. Fuson, H. Tian, H. van Besien, A.R. Conrad, M.J. Tubergen, H.D. Rudolph, and J. Demaison. 2013. "Microwave Spectra of the Deuterium Isotopologues of cis-Hexatriene and a Semiexperimental Equilibrium Structure." Journal of Physical Chemistry A 117(39): 9391-9400.en
dc.identifier.issn1089-5639en
dc.identifier.urihttp://hdl.handle.net/11282/334054-
dc.description.abstractMicrowave transitions and ground state rotational constants are reported for five newly synthesized deuterium isotopologues of cis-1,3,5-hexatriene (cHTE). These rotational constants along with those of the parent and the three 13C species are used with vibration–rotation constants calculated from an MP2/cc-pVTZ model to derive an equilibrium structure. That structure is improved by the mixed estimation method. In this method, internal coordinates from good-quality quantum chemical calculations (with appropriate uncertainties) are fit simultaneously with moments of inertia of the full set of isotopologues. The new structure of cHTE is confirmed to be planar and is stabilized by an interaction between the hydrogen atoms H2 and H5, which form a bond and participate in a six-membered ring. cHTE shows larger structural effects of π-electron delocalization than does butadiene with the effects being magnified in the center of the molecule. Thus, strong structural evidence now exists for an increase in π-electron delocalization as the polyene chain lengthens.en
dc.language.isoen_USen
dc.publisherAmerican Chemical Societyen
dc.identifier.doi10.1021/jp311035cen
dc.subject.departmentChemistryen
dc.titleMicrowave Spectra of the Deuterium Isotopologues of cis-Hexatriene and a Semiexperimental Equilibrium Structureen
dc.typeArticleen
dc.identifier.journalJournal of Physical Chemistry Aen
dc.identifier.volume117en
dc.identifier.issue39en
dc.identifier.startpage9391en
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