Vibrational frequencies and infrared intensities of the hydrogen-bonded complexes of nitrous acid with ethers: ab initio and DFT studies

Dimitrova, Yordanka; Slavova, Iva

doi:10.1016/j.saa.2004.07.038

Cited by 6 publications

(3 citation statements)

References 19 publications

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“…Several combined DFT and pseudopotential vibrational studies have shown a good agreement between calculated and experimental data. 26,39 Table 3 outlines the calculated and experimental IR and Raman frequencies for the Mo 3 M′S 4 (M′ ) Ni or Cu) cores, together with their corresponding vibrational modes. Spectroscopic results for Mo 3 S 4 have been included for comparison.…”

Section: Resultsmentioning

confidence: 99%

Combined Theoretical and Experimental Analysis of the Bonding in the Heterobimetallic Cubane-Type Mo₃NiS₄and Mo₃CuS₄Core Clusters

et al. 2007

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X-ray structural data for the cubane-type clusters [Mo3CuS4(dmpe)3Cl4](+) and Mo3NiS4(dmpe)3Cl4 (dmpe = 1,2-bis(dimethylphosphino)ethane) with 16 metal electrons have been compared with optimized structural parameters calculated using "ab initio" methodologies. Compound Mo3NiS4(dmpe)3Cl4 crystallizes in the cubic noncentrosymmetric space group P213 with a Mo-Ni distance of 2.647 Angstrom, that is 0.2 Angstrom shorter than the Mo-Cu bond length in the isoelectronic copper cluster. The best agreement between theory and experiments has been obtained using the B3P86 method. In order to validate the B3P86 results, accurate infrared and Raman spectra have been acquired and the vibrational modes associated to the cubane-type Mo3M'S4 (M' = Cu or Ni) unit have been assigned theoretically. The electronic changes taking place when incorporating the M' into the Mo3S4 unit have been analyzed from a theoretical and experimental perspective. The bond dissociation energies between M'-Cl and Mo3S4 fragments show that formation of [Mo3CuS4(dmpe)3Cl4](+) is 135 kcal/mol energetically less favorable than the Ni incorporation. The more robust nature of the Mo3NiS4 fragment has been confirmed by mass spectrometry. The X-ray photoelectron spectroscopy (XPS) spectra of the trimetallic and tetrametallic complexes have been measured and the obtained binding energies compared with the computed electronic populations based on topological approaches of the electron localization function (ELF). The energies and shapes of the Cu 2p and Ni 2p lines indicate formal oxidation states of Cu(I) and Ni(II). However, the reductive addition of nickel into [Mo3S4(dmpe)3Cl3](+) causes a small decrease in the Mo 3d binding energies. This fact prevents an unambiguous assignment of an oxidation state in a conventional way, a circumstance that has been analyzed through the covariance of the electronic populations associated to the C(M') core and V(Mo3Ni) and V(S(2)') valence basins where Mo3NiS4 is a particularly electronically delocalized chemical entity.

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Section: Resultsmentioning

confidence: 99%

Combined Theoretical and Experimental Analysis of the Bonding in the Heterobimetallic Cubane-Type Mo₃NiS₄and Mo₃CuS₄Core Clusters

et al. 2007

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“…The matrix infrared spectra provide very common information about the hydrogen bonding and structure of such systems. [2,5] The structures, stability and vibrational spectra of the hydrogen-bonded complexes of nitric and nitrous acids with various atmospheric bases have been studied extensively in our previous studies [12][13][14][15][16][17][18][19] by ab initio calculations at SCF and MP2 levels and density functional calculations with various basis sets.…”

Section: Introductionmentioning

confidence: 99%

Structures and Vibrational Spectra of the Hydrogen-Bonded Complexes Between Nitrous Acid and Acetone:Ab Initioand DFT Studies

Dimitrova

2010

Spectroscopy Letters

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The structures, stability, and vibrational spectra of the binary complexes formed between acetone and nitrous (trans and cis) acid have been investigated using ab initio calculations at the SCF and MP2 levels and B3LYP calculations with 6-311þþG(d,p) basis set. Full geometry optimization was made for the complexes studied. It was established that the complex (CH 3 ) 2 CO Á Á Á HONO-trans is more stable than the complex (CH 3 ) 2 CO Á Á Á HONO-cis by 0.5-0.8 kcalÁmol À1 . The accuracy of the calculations has been estimated by comparison between the predicted values of the vibrational characteristics (vibrational frequencies and infrared intensities) and the available experimental data. It was established, that the methods, used in this study are well adapted to the problem under examination. The predicted values with the B3LYP=6-311þþG(d,p) calculations are very near to the results, obtained with p). The calculated frequency shift Dn(OÀH) for the complex (CH 3 ) 2 CO Á Á Á HONO-trans (1A) is larger than for the complex (CH 3 ) 2 CO Á Á Á HONO-cis (1B). In the same time the intensity of this vibration increases dramatically upon hydrogen bonding. The calculated increase for the complex 1A is up to 15 times and for the complex 1B is up to 30 times. The changes in the vibrational characteristics (vibrational frequencies and infrared intensities) of (CH 3 ) 2 CO upon the complexation are more insignificant than the changes in the vibrational characteristics of HONO-trans and HONO-cis.

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“…Ethers [11][12][13][14][15] have been widely used as oxygen bases in studies on hydrogen bonding. The infrared spectra of hydrogen halides with ethers [11] as well as the hydrogen-bonded complexes of nitrous acid with ethers [12] have been reported. The vibrational spectrum of the dimethyl ether-water complex was particularly investigated by Barnes [13].…”

Section: Introductionmentioning

confidence: 99%

Optimized structures and vibration frequencies of the ether–water complex: a DFT and FTIR study

et al. 2009

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The infrared spectrum of ether was studied using Fourier transform infrared spectroscopy in conjunction with the density functional theory (DFT). The optimized structures and vibrational frequencies of the etherÁ(H 2 O) n (n = 1-3) complexes were obtained at B3LYP/6-31G(d) theory levels. Compared to those of free-form ether, the C-O stretching vibrational frequencies of the ether-water complexes are found to shift to red by up to 39 cm -1 with an increase in the C-O length of 0.016 Å . Meanwhile, the frequency of the O-H stretching modes of water in the complexes appears significantly redshifted to a varying degree. The DFT calculations suggest that these shifts are caused by the hydrogen bonding between ether and water.

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Vibrational frequencies and infrared intensities of the hydrogen-bonded complexes of nitrous acid with ethers: ab initio and DFT studies

Cited by 6 publications

References 19 publications

Combined Theoretical and Experimental Analysis of the Bonding in the Heterobimetallic Cubane-Type Mo₃NiS₄and Mo₃CuS₄Core Clusters

Combined Theoretical and Experimental Analysis of the Bonding in the Heterobimetallic Cubane-Type Mo₃NiS₄and Mo₃CuS₄Core Clusters

Structures and Vibrational Spectra of the Hydrogen-Bonded Complexes Between Nitrous Acid and Acetone:Ab Initioand DFT Studies

Optimized structures and vibration frequencies of the ether–water complex: a DFT and FTIR study

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Vibrational frequencies and infrared intensities of the hydrogen-bonded complexes of nitrous acid with ethers: ab initio and DFT studies

Cited by 6 publications

References 19 publications

Combined Theoretical and Experimental Analysis of the Bonding in the Heterobimetallic Cubane-Type Mo3NiS4and Mo3CuS4Core Clusters

Combined Theoretical and Experimental Analysis of the Bonding in the Heterobimetallic Cubane-Type Mo3NiS4and Mo3CuS4Core Clusters

Structures and Vibrational Spectra of the Hydrogen-Bonded Complexes Between Nitrous Acid and Acetone:Ab Initioand DFT Studies

Optimized structures and vibration frequencies of the ether–water complex: a DFT and FTIR study

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Combined Theoretical and Experimental Analysis of the Bonding in the Heterobimetallic Cubane-Type Mo₃NiS₄and Mo₃CuS₄Core Clusters

Combined Theoretical and Experimental Analysis of the Bonding in the Heterobimetallic Cubane-Type Mo₃NiS₄and Mo₃CuS₄Core Clusters