Anharmonic Vibrational Analysis of the Infrared and Raman Gas-Phase Spectra of s-trans - and s-gauche -1,3-Butadiene

Title:
Anharmonic Vibrational Analysis of the Infrared and Raman Gas-Phase Spectra of s-trans - and s-gauche -1,3-Butadiene
Authors:
Krasnoshchekov, Sergey V.; Craig, Norman C.; Boopalachandran, Praveenkumar; Laane, Jaan; Stepanov, Nikolay F.
Abstract:
A quantum-mechanical (hybrid MP2/cc-pVTZ and CCSD(T)/cc-pVTZ) full quartic potential energy surface (PES) in rectilinear normal coordinates and the second-order operator canonical Van Vleck perturbation theory (CVPT2) are employed to predict the anharmonic vibrational spectra of s-trans- and s-gauche-butadiene (BDE). These predictions are used to interpret their infrared and Raman scattering spectra. New high-temperature Raman spectra in the gas phase are presented in support of assignments for the gauche conformer. The CVPT2 solution is based on a PES and electro-optical properties (EOP; dipole moment and polarizability) expanded in Taylor series. Higher terms than those routinely available from Gaussian09 software were calculated by numerical differentiation of quadratic force fields and EOP using the MP2/cc-pVTZ model. The integer coefficients of the polyad quantum numbers were derived for both conformers of BDE. Replacement of harmonic frequencies by their counterparts from the CCSD(T)/cc-pVTZ model significantly improved the agreement with experimental data for s-trans-BDE (root-mean-square deviation approximate to 5.5 cm(-1)). The accuracy in predicting the rather well-studied spectrum of fundamentals of s-trans-BDE assures good predictions of the spectrum of s-gauche-BDE. A nearly complete assignment of fundamentals was obtained for the gauche conformer. Many nonfundamental transitions of the BDE conformers were interpreted as well. The predictions of multiple Fermi resonances in the complex CH-stretching region correlate well with experiment. It is shown that solving a vibrational anharmonic problem through a numerical-analytic implementation of CVPT2 is a straightforward and computationally advantageous approach for medium-size molecules in comparison with the standard second-order vibrational perturbation theory (VPT2) based on analytic expressions.
Citation:
Krasnoshchekov, S.V., N.C. Craig, P. Boopalachandran, J. Laane, and N.F. Stepanov. 2015. "Anharmonic Vibrational Analysis of the Infrared and Raman Gas-Phase Spectra of s-trans- and s-gauche-1,3-Butadiene." The Journal of Physical Chemistry A 119(43): 10706-10723.
Publisher:
American Chemical Society
DATE ISSUED:
2015-10-29
Department:
Chemistry
Type:
Article
PUBLISHED VERSION:
10.1021/acs.jpca.5b07650
Additional Links:
http://pubs.acs.org/doi/10.1021/acs.jpca.5b07650
PERMANENT LINK:
http://hdl.handle.net/11282/593490

Full metadata record

DC FieldValue Language
dc.contributor.authorKrasnoshchekov, Sergey V.en
dc.contributor.authorCraig, Norman C.en
dc.contributor.authorBoopalachandran, Praveenkumaren
dc.contributor.authorLaane, Jaanen
dc.contributor.authorStepanov, Nikolay F.en
dc.date.accessioned2016-01-14T16:57:06Zen
dc.date.available2016-01-14T16:57:06Zen
dc.date.issued2015-10-29en
dc.identifier.citationKrasnoshchekov, S.V., N.C. Craig, P. Boopalachandran, J. Laane, and N.F. Stepanov. 2015. "Anharmonic Vibrational Analysis of the Infrared and Raman Gas-Phase Spectra of s-trans- and s-gauche-1,3-Butadiene." The Journal of Physical Chemistry A 119(43): 10706-10723.en
dc.identifier.issn1089-5639en
dc.identifier.urihttp://hdl.handle.net/11282/593490en
dc.description.abstractA quantum-mechanical (hybrid MP2/cc-pVTZ and CCSD(T)/cc-pVTZ) full quartic potential energy surface (PES) in rectilinear normal coordinates and the second-order operator canonical Van Vleck perturbation theory (CVPT2) are employed to predict the anharmonic vibrational spectra of s-trans- and s-gauche-butadiene (BDE). These predictions are used to interpret their infrared and Raman scattering spectra. New high-temperature Raman spectra in the gas phase are presented in support of assignments for the gauche conformer. The CVPT2 solution is based on a PES and electro-optical properties (EOP; dipole moment and polarizability) expanded in Taylor series. Higher terms than those routinely available from Gaussian09 software were calculated by numerical differentiation of quadratic force fields and EOP using the MP2/cc-pVTZ model. The integer coefficients of the polyad quantum numbers were derived for both conformers of BDE. Replacement of harmonic frequencies by their counterparts from the CCSD(T)/cc-pVTZ model significantly improved the agreement with experimental data for s-trans-BDE (root-mean-square deviation approximate to 5.5 cm(-1)). The accuracy in predicting the rather well-studied spectrum of fundamentals of s-trans-BDE assures good predictions of the spectrum of s-gauche-BDE. A nearly complete assignment of fundamentals was obtained for the gauche conformer. Many nonfundamental transitions of the BDE conformers were interpreted as well. The predictions of multiple Fermi resonances in the complex CH-stretching region correlate well with experiment. It is shown that solving a vibrational anharmonic problem through a numerical-analytic implementation of CVPT2 is a straightforward and computationally advantageous approach for medium-size molecules in comparison with the standard second-order vibrational perturbation theory (VPT2) based on analytic expressions.en
dc.language.isoen_USen
dc.publisherAmerican Chemical Societyen
dc.identifier.doi10.1021/acs.jpca.5b07650en
dc.relation.urlhttp://pubs.acs.org/doi/10.1021/acs.jpca.5b07650en
dc.subject.departmentChemistryen_US
dc.titleAnharmonic Vibrational Analysis of the Infrared and Raman Gas-Phase Spectra of s-trans - and s-gauche -1,3-Butadieneen_US
dc.typeArticleen
dc.identifier.journalThe Journal of Physical Chemistry Aen
dc.identifier.volume119en_US
dc.identifier.issue43en_US
dc.identifier.startpage10706en_US
dc.rightsArchived with thanks to The Journal of Physical Chemistry Aen
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