An approach to the structure and vibrational analysis of cis- and trans-3-chlorostyrene through IR/Raman and INS spectroscopies and theoretical ab initio/DFT calculations

Granadino‐Roldán, José M.; Fernández-Gómez, Manuel; Navarro, Amparo; Ruiz, Arturo; Jayasooriya, Upali A.

doi:10.1039/b314243d

Cited by 10 publications

(4 citation statements)

References 41 publications

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“…The assignments of C-Cl stretching and deformation vibrations have been made on the basis of DFT calculations and by comparison with similar molecules such as 2,4-dichloroaniline, 4-chloro-Nmethylaniline and cis-trans-3-chlorostyrene [30]. Mooney [31,32] assigned the bands appearing in the range of 1129-480 cm −1 to the vibrations of C-X group (X = Cl, Br, I).…”

Section: C-cl Vibrationsmentioning

confidence: 99%

Molecular structure and vibrational spectra of o-chlorotoluene, m-chlorotoluene, and p-chlorotoluene by ab initio HF and DFT calculations

Wang

Ren

Wang

et al. 2011

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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Section: C-cl Vibrationsmentioning

confidence: 99%

Molecular structure and vibrational spectra of o-chlorotoluene, m-chlorotoluene, and p-chlorotoluene by ab initio HF and DFT calculations

Wang

Ren

Wang

et al. 2011

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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“…In this work we have performed geometry optimizations at different levels of theory, MP2 and DFT, with different basis sets in order to study not only the planarity of the molecule free of any intermolecular interaction but also to get an estimate of the performance of these theoretical methods in the estimation of the torsional barrier of this system. The influence of the number, nature and positions of the ring substituents has been assessed by comparing with other halostyrene derivatives already studied − although it can be anticipated that in the current case, the increased hindrance due to the occurrence of chlorine atoms in positions α−α‘ is expected to have a significant effect on both magnitude and shape of the torsion barrier.…”

Section: Introductionmentioning

confidence: 99%

Molecular Structure, Vinyl Rotation Barrier, and Vibrational Dynamics of 2,6-Dichlorostyrene. A Theoretical and Experimental Research

et al. 2007

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The molecular structure of 2,6-dichlorostyrene has been analyzed at MP2 and DFT levels using different basis sets concluding in a nonplanar geometry. The influence of either the level of theory or the nature of the substituent has been assessed. The vinyl-phenyl torsion barrier has also been investigated as a function of level of theory. The ultimate factors responsible for the torsion barrier have been studied using two different partitioning schemes, i.e., the total electronic potential energy and the natural bond orbital, NBO. A topological analysis of the electron density within the atom-in-molecule, AIM, theory predicts soft intramolecular chlorine (ring)-hydrogen (vinyl) contacts when the system becomes planar. A first complete vibrational study has been performed using theoretical data and experimental vibrational frequencies from IR, Raman and, for the first time, inelastic neutron scattering, INS, spectra. The new assignment proposed is based on a scaled quantum mechanical, SQM, force field and the wavenumber linear scaling, WLS, approach.

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“…However, all ab initio calculations predict the twisted structure to be <1 kcal/mol lower in energy than the planar form, so even the inclusion of zero-point vibrational and temperature effects could change the result in favor of the planar structure. Most experimental studies have concluded that, in the ground electronic state, the styrene monomer is planar. , …”

Section: Introductionmentioning

confidence: 99%

“…Most experimental studies have concluded that, in the ground electronic state, the styrene monomer is planar. 14,15 An ab initio (HF and configuration interaction singles (CIS), with MP2 correction) study by Zilberg and Hass 16 described the vibrational spectra of the ground and first excited singlet states of styrene and -methyl styrene. It was found that the ground state of the molecule has a broad shallow torsional potential.…”

Section: Introductionmentioning

confidence: 99%

Modeling Styrene−Styrene Interactions

Adamovic

Lamm

et al. 2005

J. Phys. Chem. A

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This study is the first step in the systematic investigation of substituted (carboxyl) polystyrene nanoparticles. Understanding the fundamental interactions between the p-carboxyl styrene monomers, where an ethyl group is used instead of a vinyl group (referenced, for convenience, as "p-carboxyl styrene"), provides the basic information needed to construct potentials for nanoparticles composed of these monomers. In this work, lowenergy isomers of p-carboxyl styrene dimer were studied. The dimer structures and their relative and binding energies were determined using both MÃ¸ller-Plesset second-order perturbation theory (MP2) and the general effective fragment potential (EFP2) method. Sections of the intermolecular potential energy surface (PES) of the p-carboxylated styrene dimer in its global minimum orientation were also determined. As expected, double hydrogen bonding between the two carboxylic groups provides the strongest interaction in this system, followed by isomers with a single H-bond and strong benzene ring-benzene ring (Ï€-Ï€) type interactions. Generally, the EFP2 method reproduces the MP2 geometries and relative energies with good accuracy, so it appears to be an efficient alternative to the correlated ab initio methods, which are too computationally demanding to be routinely used in the study of the more-complex polymeric systems of interest. This study is the first step in the systematic investigation of substituted (carboxyl) polystyrene nanoparticles. Understanding the fundamental interactions between the p-carboxyl styrene monomers, where an ethyl group is used instead of a vinyl group (referenced, for convenience, as "p-carboxyl styrene"), provides the basic information needed to construct potentials for nanoparticles composed of these monomers. In this work, lowenergy isomers of p-carboxyl styrene dimer were studied. The dimer structures and their relative and binding energies were determined using both Møller-Plesset second-order perturbation theory (MP2) and the general effective fragment potential (EFP2) method. Sections of the intermolecular potential energy surface (PES) of the p-carboxylated styrene dimer in its global minimum orientation were also determined. As expected, double hydrogen bonding between the two carboxylic groups provides the strongest interaction in this system, followed by isomers with a single H-bond and strong benzene ring-benzene ring (π-π) type interactions. Generally, the EFP2 method reproduces the MP2 geometries and relative energies with good accuracy, so it appears to be an efficient alternative to the correlated ab initio methods, which are too computationally demanding to be routinely used in the study of the more-complex polymeric systems of interest.

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An approach to the structure and vibrational analysis of cis- and trans-3-chlorostyrene through IR/Raman and INS spectroscopies and theoretical ab initio/DFT calculations

Cited by 10 publications

References 41 publications

Molecular structure and vibrational spectra of o-chlorotoluene, m-chlorotoluene, and p-chlorotoluene by ab initio HF and DFT calculations

Molecular structure and vibrational spectra of o-chlorotoluene, m-chlorotoluene, and p-chlorotoluene by ab initio HF and DFT calculations

Molecular Structure, Vinyl Rotation Barrier, and Vibrational Dynamics of 2,6-Dichlorostyrene. A Theoretical and Experimental Research

Modeling Styrene−Styrene Interactions

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