Vibrational study of fluorobenzene and its solvation with methanol via polarized Raman measurements and quantum chemical calculations

Singh, Shweta; Singh, Dheeraj K.; Srivastava, Sunil K.; Asthana, B. P.

doi:10.1016/j.vibspec.2010.08.011

Cited by 25 publications

(4 citation statements)

References 43 publications

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“…In addition, Tables S1 and S2 (Supporting Information) give a detailed overview of the PEDs (in percent) of these IR or Raman active fundamental modes based solely on the B3LYP/6-311++G(d,p) calculations. However, the complete vibrational analysis of the observed modes is also based on our earlier investigations of N -benzylamino(boronphenyl)methylphosphonic acid analogues, fluorobenzene, , fluorophenylboronic acids, ,, benzaldehyde derivatives, and aromatic formyl compounds. − …”

Section: Results and Discussionmentioning

confidence: 99%

Influence of Substituent Type and Position on the Adsorption Mechanism of Phenylboronic Acids: Infrared, Raman, and Surface-Enhanced Raman Spectroscopy Studies

et al. 2013

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This paper shows systematic spectroscopic studies using Fourier-transform infrared absorption (FT-IR), Fourier-transform Raman (FT-Raman), and surface-enhanced Raman (SERS) in an aqueous silver sol of fluoro and formyl analogues of phenylboronic acids: 2-fluorophenylboronic acid (2-F-PhB(OH)2), 3-fluorophenylboronic acid (3-F-PhB(OH)2), 4-fluorophenylboronic acid (4-F-PhB(OH)2), 2-formylphenylboronic acid (2-CHO-PhB(OH)2), 3-formylphenylboronic acid (3-CHO-PhB(OH)2), and 4-formylphenylboronic acid (4-CHO-PhB(OH)2). To produce an extensive table of vibrational spectra, density functional theory (DFT) calculations with the B3LYP method at the 6-311++G(d,p) level of theory were performed for the ground state geometry of the most stable species, dimers in cis-trans conformation. On the basis of the SERS spectral profile, the adsorption modes of the phenylboronic acid isomers were proposed. The type of substituent and its position in the phenyl ring have a strong influence on the geometry of isomers on the silver nanoparticle's surface. This effect was especially evident in the case of 4-CH-PhB(OH)2, for which dearomatization of the phenyl ring took place upon adsorption.

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Section: Results and Discussionmentioning

confidence: 99%

Influence of Substituent Type and Position on the Adsorption Mechanism of Phenylboronic Acids: Infrared, Raman, and Surface-Enhanced Raman Spectroscopy Studies

et al. 2013

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“…In comparison to the B3LYP and D-B3LYP functionals, the long range dispersion-corrected functional wB97X-D provides the best accuracy for thermochemistry, kinetics, and noncovalent interactions . The split valance basis set 6-311++G(d,p) was employed in all presented calculations due to its tremendous performance in molecular interactions. ,,− The Gaussian 09 suite of programs was used for all computations linked with the GaussView 5.1 program for preparing the input geometry as well as visualizing the output results.…”

Section: Theorymentioning

confidence: 99%

Interplay of Different Moieties in the Binary System 1-Ethyl-3-methylimidazolium Trifluoromethanesulfonate/Water Studied by Raman Spectroscopy and Density Functional Theory Calculations

et al. 2019

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The present work reports new insights into specific interactions in aqueous solutions of the ionic liquid (IL) 1-ethyl-3methylimidazolium trifluoromethanesulfonate (C 2 mimTfO). A systematic investigation based on a combination of Raman spectroscopy and density functional theory (DFT) calculations shows evidence of self-encapsulation of the ionic moiety. Raman spectroscopy reveals preferred interactions between water molecules and the TfO − anions. The comparison of the experimental results with dispersion-corrected DFT calculations, which yield the predictions of the possible conformers of the cation−water, anion−water, and cation−anion−water structures, strongly supports the hypotheses of site-selective IL/water interactions. The obtained results allow for a detailed discussion of the nature and strength of the molecular interactions. It is shown that the TfO − anion establishes a preferred interaction with water, whereas the vibrational band at 3118 cm −1 for C− H motion at the C(2) position, the most acidic site for cation and anion interaction, does not indicate any specific energy shift, when adding water to the IL. This finding gives evidence for a self-protective microstructure of the molecules of C 2 mimTfO in an aqueous environment. In contrast to other ILs reported in the literature, there is no evidence of an increasing cation−anion distance in the IL ion-pair when increasing the water content. Instead, the C 2 mimTfO molecules undergo a perfect rearrangement, allowing interactions at other molecular sites with higher selectivity. A direct exposure to water at the cation− anion interacting site (C(2) position) is avoided. Ultimately, we show that clusters of ion-pair dimers solvated with water exhibit a more stable geometry compared to the hydrated single ion-pairs, and our calculations correctly reproduce the experimental findings.

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“…The long-range dispersion-corrected functional wB97X-D yields more satisfying accuracy for thermochemistry, kinetics, and noncovalent interactions than the B3LYP and D-B3LYP functionals . The high level basis set 6-311++G(d,p) was used in all the calculations, as it performed well in the prediction of molecular interactions. − The Gaussian 09 suite of programs was used for all the computations, and the GaussView 5.1 program was used to visualize the structures.…”

Section: Computationsmentioning

confidence: 99%

Molecular Structure and Interactions in the Ionic Liquid 1-Ethyl-3-methylimidazolium Trifluoromethanesulfonate

et al. 2016

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Quantum chemical theory (DFT and MP2) and vibrational spectroscopy (ATR-IR and Raman) were employed to investigate the electronic structure and molecular interactions in the room-temperature ionic liquid 1-ethyl-3-methylimidazolium trifluoromethanesulfonate. Various possible conformers of a cation-anion pair based on their molecular interactions were simulated in the gas phase. All the different theoretical (MP2, B3LYP, and the dispersion-corrected wB97XD) methods assume the same ion-pair conformation for the lowest energy state. Basis set superimpose error (BSSE) correction was also introduced by using the counterpoise method. Strong C-H···O interactions between the most acidic hydrogen atom of the cation imidazole ring (C2H) and the oxygen atom of the anion were predicted where the anion is located at the top of (C2H). In this case, methyl and alkyl groups also interact with the anion in the form of a C-H···O hydrogen bond. Interestingly, the dispersion-corrected methodology neglects the C4/C5-H···O and C-H···F interaction in the ion-pair calculations. The theoretical results were compared with the experimental observations from Raman scattering and ATR-IR absorption spectroscopy, and the predictions of the molecular interactions in the vibrational spectra were discussed. The wavenumber shifts of the characteristic vibrations relative to the free cation and anion are explained by estimating the geometric parameters as well as the difference in the natural bond orbital (NBO) charge density.

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Vibrational study of fluorobenzene and its solvation with methanol via polarized Raman measurements and quantum chemical calculations

Cited by 25 publications

References 43 publications

Influence of Substituent Type and Position on the Adsorption Mechanism of Phenylboronic Acids: Infrared, Raman, and Surface-Enhanced Raman Spectroscopy Studies

Influence of Substituent Type and Position on the Adsorption Mechanism of Phenylboronic Acids: Infrared, Raman, and Surface-Enhanced Raman Spectroscopy Studies

Interplay of Different Moieties in the Binary System 1-Ethyl-3-methylimidazolium Trifluoromethanesulfonate/Water Studied by Raman Spectroscopy and Density Functional Theory Calculations

Molecular Structure and Interactions in the Ionic Liquid 1-Ethyl-3-methylimidazolium Trifluoromethanesulfonate

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