Vibrational computations beyond the harmonic approximation: Performances of the B3LYP density functional for semirigid molecules

Carbonnière, Philippe; Lucca, Tecla; Pouchan, Claude; Rega, Nadia; Barone, Vincenzo

doi:10.1002/jcc.20170

Cited by 187 publications

(180 citation statements)

References 29 publications

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“…They yield very good results for organic molecules and their results agree very well with experimental data [44,[131][132][133]. Therefore, they are widely-used and tested.…”

Section: Appendix B1 Band Structure and Optical Functionssupporting

confidence: 62%

Infrared Investigations of the Neutral-Ionic Phase Transition in TTF-CA and Its Dynamics

Dressel

Peterseim

2017

Crystals

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Abstract:The neutral-ionic phase transition in TTF-CA was investigated by steady-state and time-resolved infrared spectroscopy. We describe the growth of high-quality single crystals and their characterization. Extended theoretical calculations were performed in order to obtain the band structure, the molecular vibrational modes and the optical spectra along all crystallographic axes. The theoretical results are compared to polarization-dependent infrared reflection experiments. The temperature-dependent optical conductivity is discussed in detail. We study the photo-induced phase transition in the vicinity of thermally-induced neutral-ionic transition. The observed temporal dynamics of the photo-induced states is attributed to the random-walk of neutral-ionic domain walls. We simulate the random-walk annihilation process of domain walls on a one-dimensional chain.

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“…They yield very good results for organic molecules and their results agree very well with experimental data [44,[131][132][133]. Therefore, they are widely-used and tested.…”

Section: Appendix B1 Band Structure and Optical Functionssupporting

confidence: 62%

Infrared Investigations of the Neutral-Ionic Phase Transition in TTF-CA and Its Dynamics

Dressel

Peterseim

2017

Crystals

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“…The progressions of the 2ν 4 and ν 2 + ν 4 intensity relative to ν 3 are fairly traduced. The first decreases while the second increases: 37%, 31%, 28% of ν 3 character in the 2ν 4 and 9%, 11%, and 13% in the ν 2 + ν 4 for the 11 hydrides series. Concerning the 11 deuterides, we report 13%, 15%, and 12% of ν 3 character for 2ν 4 and 21%, 22%, and 25% for ν 2 + ν 4 .…”

Section: Resultsmentioning

confidence: 95%

“…As mentioned above, the accuracy of the DFT model seems not involved since a such model leads to results typically fitting 11,19,20 as well as on larger organic systems (benzene, pyrrole, furan, thiophene, azabenzenes, and uracyle). 11,[21][22][23] The discrepancies observed shows that surrounding in a solid strongly hinders the motions of vibrations of the central species which explains the too low calculated energies by considering the naked form of BH 4 -with regard to experimental values. This is in agreement with experimental investigation of alkali borohydride series, where frequencies of the anion clearly decrease while the octahedral site is widened from KBH 4 to CsBH 4 .…”

Section: Resultsmentioning

confidence: 99%

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Fermi Resonances of Borohydrides in a Crystalline Environment of Alkali Metals

Carbonnière

Hagemann

2006

J. Phys. Chem. A

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Vibrational spectra of BH 4-and its isotopic analogues in a crystalline environment of alkali metals cations (K + , Rb + , Cs + ) have been investigated beyond the harmonic approximation using a variational approach supported by computations of B3LYP type anharmonic force fields. From the comparison of the observed and simulated IR spectra, the influence of the anharmonic couplings on the band position and on the relative intensity of the allowed vibrational transitions is discussed. Here, the effect of the crystalline environment induces a blue shift of about 50 and 100 cm -1 respectively for the bending and stretching modes of BH 4 -. Furthermore, anharmonic effects, which are exclusively well reproduced by a variational approach, are needed to yield reliable positions and relative amplitudes of IR allowed combination and overtone transitions. This leads to theoretical results fitting their experimental counterpart between 6 and 30 cm -1 in the investigated series.

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“…molecules [118]. The calculations were carried out for the isolated molecule with the C 1 and the D 2h symmetry suggested by Meneghetti et al [59].…”

Section: Discussionmentioning

confidence: 99%

Comprehensive Optical Investigations of Charge Order in Organic Chain Compounds (TMTTF)2X

et al. 2012

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Charge ordering in the (TMTTF) 2 X salts with centrosymmetric anions (X = PF − 6 , AsF − 6 , SbF − 6 ) leads to a ferroelectric state around 100 K. For the first time and in great completeness, the intra-and intermolecular vibrational modes of (TMTTF) 2 X have been investigated by infrared and Raman spectroscopy as a function of temperature and pressure for different polarizations. In this original paper, we explore the development and amount of charge disproportionation and the coupling of the electronic degrees of freedom to the counterions and the underlying lattice. The methyl groups undergo changes with temperature that are crucial for the anion cage formed by them. We find that the coupling of the TMTTF molecules to the hexafluorine anions changes upon cooling and especially at the charge-order transition, indicating a distortion of the anion. Additional features are identified that are caused by the anharmonic potential. The spin-Peierls transition entails additional modifications in the charge distribution. To complete the discussion, we also add the vibrational frequencies and eigenvectors based on ab-initio quantum-chemical calculations.

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Vibrational computations beyond the harmonic approximation: Performances of the B3LYP density functional for semirigid molecules

Cited by 187 publications

References 29 publications

Infrared Investigations of the Neutral-Ionic Phase Transition in TTF-CA and Its Dynamics

Infrared Investigations of the Neutral-Ionic Phase Transition in TTF-CA and Its Dynamics

Fermi Resonances of Borohydrides in a Crystalline Environment of Alkali Metals

Comprehensive Optical Investigations of Charge Order in Organic Chain Compounds (TMTTF)2X

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