Hydrogen Bonding in the Organic Ferroelectric Croconic Acid: Insights from Experiment and First-Principles Modelling

Fernández-Alonso, Félix; Gutmann, Matthias J.; Mukhopadhyay, Sanghamitra; Jochym, Dominik B.; Refson, Keith; Jura, Marek; Krzystyniak, M.; Jiménez‐Ruiz, Mónica; Wagner, Armin

doi:10.7566/jpsjs.82sa.sa001

Cited by 12 publications

(19 citation statements)

References 30 publications

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“…[7][8][9][10] is blue shifted by about 150 cm −1 in the calculated spectra. These dominant vibrations, as observed in INS at 880 and 900 cm −1 , are predicted as the out-of-plane bending modes of protons for O-H(T)-O and O-H…”

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confidence: 84%

“…Strong and flexible hydrogen bonds in croconic acid crystal support a Jahn-Teller type distortion leading to strong polarisation at room temperatures [7]. Inelastic neutron scattering (INS) along with first principles density functional theory (DFT) based lattice and molecular dynamics calculations help to underpin the dynamics of protons of its hydrogen bonds [8][9][10]. As a continuation of these investigations, in this article the focus is to investigate the vibrational modes related to hydrogen bonds in CBDC (1-cyclobutene-1,2dicarboxylic acid, C 6 H 8 O 4 ), another hydrogen-bonded molecular crystal showing ferroelectric properties at room temperatures [2,4].…”

Section: Introductionmentioning

confidence: 99%

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Identification of normal modes responsible for ferroelectric properties in organic ferroelectric CBDC

Mukhopadhyay

2019

J. Phys. Commun.

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Structure and dynamics of hydrogen bonded organic ferroelectric CBDC (1-cyclobutene-1,2dicarboxylic acid, C 6 H 8 O 4 ) have been investigated using inelastic neutron scattering (INS) spectroscopy and first principles lattice dynamics. Vibrational modes of O-H-O bending, related with two different types of hydrogen bonds, inter and intra-molecular, are manifested as two sets of doublets in the range of 900-1400 cm −1 in the INS spectrum. First principles density functional theory (DFT) is used to assign these doublets to out-of-the-plane and in-plane vibrations of these two types of O-H-O bending modes. Correlating structure and dynamics we find that although the local structures of the hydrogen bonded protons are similar, their medium range order may influence their vibrational frequencies. Vibrational modes of non-hydrogen bonded protons also are assigned separately in the spectrum. Comparing the calculated and the experimental INS spectra it is predicted that hydrogen bonded O-H bonds are more anharmonic than non-hydrogen bonded C-H bonds. From the calculated Born effective charge tensor it is predicted that inter-molecular hydrogen bonds contribute more to the ferroelectric polarisation of CBDC than intra-molecular ones. A large LO-TO splitting of the O-H stretching mode at 2471 cm −1 is identified with the mode that has significant contribution to the ferroelectric polarisation. As this mode is sensitive to long range Coulomb interactions and is responsible for ferroelectric properties of the material, vibrational spectroscopy combined with DFT calculations is proposed as a characterisation tool to investigate ferroelectric properties in the CBDC molecular crystal.

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confidence: 84%

Section: Introductionmentioning

confidence: 99%

Identification of normal modes responsible for ferroelectric properties in organic ferroelectric CBDC

Mukhopadhyay

2019

J. Phys. Commun.

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“…2 Ferroelectricity in CA remains almost constant in the temperature range 4-400 K, which is a remarkable phenomenon for a hydrogen-bonded molecular crystal. In this and previous works, 3,4 we seek to obtain an atomistic understanding of this organic ferroelectric material via the use of first-principles computational modelling in conjunction with experiment.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen-bond structure and anharmonicity in croconic acid

Mukhopadhyay

Gutmann

Fernandez-Alonso

2014

Phys. Chem. Chem. Phys.

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First-principles molecular dynamics simulations and neutron-scattering experiments have been employed to investigate the structure and underlying vibrational motions in croconic acid as a function of temperature over the range 4-400 K. Calculated hydroxyl-bond distances were within 4% of the experimentally determined bond lengths. Temperature-dependent structures have been explored using large-scale molecular dynamics simulations. From the calculated radial distribution functions, it is found that medium-range order associated with O···H and O···O correlations are affected by an increase in temperature, yet the characteristic long-range layered structure of this material remains unaltered. Hydrogen-bond anharmonicity has been assessed from the molecular dynamics simulations, showing a red shift of ca. 50 cm(-1) of the O-H stretch frequency relative to quasi-harmonic results. This shift shows the importance of anharmonic corrections on hydrogen bonds in solid croconic acid.

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“…The similarity of design also means that VISION should also enjoy negligible backgrounds. In addition, the new instrument IN1-Lagrange at ILL [12] delivers a much higher average flux than TOSCA (and possibly even more than VISION), as inferred from recent studies on this instrument by some of the authors [13,14]. However, the resolution of IN1-Lagrange EPJ Web of Conferences remains comparable to TFXA (i.e., similar to that of most currently operating instruments).…”

Section: Introductionmentioning

confidence: 98%

Monte carlo simulations of the TOSCA spectrometer: Assessment of current performance and future upgrades

Pinna

Rudić

Parker

et al. 2015

EPJ Web of Conferences

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Abstract. We describe and assess the performance of a detailed computational description of the high-resolution TOSCA spectrometer at ISIS using neutron-transport Monte Carlo simulations. Extensive calculations using the McStas software package have been performed using the present instrument geometry and compared with available experimental data. The agreement between expected and measured performance is satisfactory in terms of the incident flux spectrum, associated time structure, and spectroscopic resolution. Encouraged by these results, we also consider the upgrade of the primary spectrometer with a tapered high-m guide. This instrument development offers the exciting prospects of providing order-of-magnitude gains in detected neutron flux over the energy-transfer range of the instrument whilst preserving its outstanding spectroscopic capabilities.

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Hydrogen Bonding in the Organic Ferroelectric Croconic Acid: Insights from Experiment and First-Principles Modelling

Cited by 12 publications

References 30 publications

Identification of normal modes responsible for ferroelectric properties in organic ferroelectric CBDC

Identification of normal modes responsible for ferroelectric properties in organic ferroelectric CBDC

Hydrogen-bond structure and anharmonicity in croconic acid

Monte carlo simulations of the TOSCA spectrometer: Assessment of current performance and future upgrades

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