Computationally Assisted (Solid-State Density Functional Theory) Structural (X-ray) and Vibrational Spectroscopy (FT-IR, FT-RS, TDs-THz) Characterization of the Cardiovascular Drug Lacidipine

Drużbicki, Kacper; Mielcarek, Jadwiga; Kiwilsza, Anna; Toupet, Loı̈c; Collet, Éric; Pajzderska, A.; Wąsicki, J.

doi:10.1021/acs.cgd.5b00251

Cited by 25 publications

(36 citation statements)

References 55 publications

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“…Recently, by using the full electronic calculations 78 (PBE/6-31++G(d,p)), we were able to show that such systematic error partially comes from the use of normconserving pseudopotentials. 79 In line with our previous findings, 65 the fixed-cell PBE calculations call for the use of a uniform scale factor of ca. 1.015, for the medium-wavenumber range.…”

Section: The Journal Of Physical Chemistry Bsupporting

confidence: 83%

Experimental (X-ray, ¹³C CP/MAS NMR, IR, RS, INS, THz) and Solid-State DFT Study on (1:1) Co-Crystal of Bromanilic Acid and 2,6-Dimethylpyrazine

et al. 2015

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A combined structural, vibrational spectroscopy, and solid-state DFT study of the hydrogen-bonded complex of bromanilic acid with 2,6-dimethylpyrazine is reported. The crystallographic structure was determined by means of low-temperature single-crystal X-ray diffraction, which reveals the molecular units in their native protonation states, forming one-dimensional infinite nets of moderate-strength O···H-N hydrogen bonds. The nature of the crystallographic forces, stabilizing the studied structure, has been drawn by employing the noncovalent interactions analysis. It was found that, in addition to the hydrogen bonding, the intermolecular forces are dominated by stacking interactions and C-H···O contacts. The thermal and calorimetric analysis was employed to probe stability of the crystal phase. The structural analysis was further supported by a computationally assisted (13)C CP/MAS NMR study, providing a complete assignment of the recorded resonances. The vibrational dynamics was explored by combining the optical (IR, Raman, TDs-THz) and inelastic neutron scattering (INS) spectroscopy techniques with the state-of-the-art solid-state density functional theory (DFT) computations. Despite the quasi-harmonic approximation assumed throughout the study, an excellent agreement between the theoretical and experimental data was achieved over the entire spectral range, allowing for a deep and possibly thorough understanding of the vibrational characteristics of the system. Particularly, the significant influence of the long-range dipole coupling on the IR spectrum has been revealed. On the basis of a wealth of information gathered, the recent implementation of a dispersion-corrected linear-response scheme has been extensively examined.

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Section: The Journal Of Physical Chemistry Bsupporting

confidence: 83%

Experimental (X-ray, ¹³C CP/MAS NMR, IR, RS, INS, THz) and Solid-State DFT Study on (1:1) Co-Crystal of Bromanilic Acid and 2,6-Dimethylpyrazine

et al. 2015

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“…Nevertheless, CASTEP geometrical parameters present some well-known limitations of PBE calculations. The C=O bond length is clearly overestimated-leading to the underestimation of the C=O stretching mode, already discussed elsewhere [2,8]-and the pi-stacking distance evidences the expected bias to large values: this distance would deviate to physically meaningless values if not constrained by cell dimensions [2]. Representation of 4-phenylbenzaldehyde, with the atom labeling used throughout the text (left) and fragment of the crystal structure, evidencing the two types of dimer present in the crystal (right) [21].…”

Section: Figurementioning

confidence: 69%

“…The inter-ring torsional potential for the isolated molecule (G09) is dominated by a V 4 component, with significant contributions from V 2 , V 6 and V 8 (Figure 5, bottom panel). However, the calculated torsional frequency of 70 cm −1 can be obtained from a simplified approach, assuming a pure V 4 term of ca.…”

Section: Large Amplitude Low Wavenumber Motionsmentioning

confidence: 99%

“…The use of periodic density functional calculations (periodic DFT) to address the vibrational spectra of molecular crystals is becoming increasingly popular [1][2][3][4][5][6][7][8][9][10][11][12]. In fact, the periodic DFT approach, although originally developed to deal with extended inorganic systems, was found to be highly efficient in predicting the vibrational spectra of molecular crystals [13].…”

Section: Introductionmentioning

confidence: 99%

“…In fact, the periodic DFT approach, although originally developed to deal with extended inorganic systems, was found to be highly efficient in predicting the vibrational spectra of molecular crystals [13]. Periodic methods-available through programs such as VASP [14], CRYSTAL [15,16] and CASTEP [17]-are often used to assist vibrational assignments of infrared and inelastic neutron scattering (INS) spectra of molecular crystals [1,2,[6][7][8][9]18]. Vibrational spectroscopy with neutrons provides information not accessible from the optical techniques (IR and Raman), due to the absence of selection rules.…”

Section: Introductionmentioning

confidence: 99%

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Vibrational Dynamics of Crystalline 4-Phenylbenzaldehyde from INS Spectra and Periodic DFT Calculations

et al. 2020

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The present work emphasizes the value of periodic density functional theory (DFT) calculations in the assessment of the vibrational spectra of molecular crystals. Periodic calculations provide a nearly one-to-one match between the calculated and observed bands in the inelastic neutron scattering (INS) spectrum of crystalline 4-phenylbenzaldehyde, thus validating their assignment and correcting previous reports based on single molecule calculations. The calculations allow the unambiguous assignment of the phenyl torsional mode at ca. 118–128 cm−1, from which a phenyl torsional barrier of ca. 4000 cm−1 is derived, and the identification of the collective mode involving the antitranslational motion of CH···O bonded pairs, a hallmark vibrational mode of systems where C-H···O contacts are an important feature.

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Vibrational Response of Felodipine in the THz Domain: Optical and Neutron Spectroscopy Versus Plane-Wave DFT Modeling

Łuczyńska

Drużbicki

Runka

et al. 2019

J Infrared Milli Terahz Waves

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We present a joint experimental and computational terahertz (THz) spectroscopy study of the most stable polymorph (form I) of an antihypertensive pharmaceutical solid, felodipine (FLD). The vibrational response has been analyzed at room temperature by combining optical (THz-TDS, FT-IR, THz-Raman) and neutron (INS) terahertz spectroscopy. With the challenging example of a large and flexible molecular solid, we illustrate the complementarity of the experimental techniques. We show how the results can be understood by employing ab initio modeling and discuss current progress in the field. To this end, we employ plane wave formulation of density functional theory (plane wave DFT) along with harmonic lattice dynamics calculations (HLD) and ab initio molecular dynamics (AIMD) simulations. Based on a comprehensive theoretical analysis, we discover an inconsistency in the commonly accepted structural model, which can be linked to a distinct librational dynamics of the side ester chains. As a result, only a moderate agreement with the experimental spectra can be achieved. We, therefore, propose an alternative structural model, effectively accounting for the influence of the large-amplitude librations and allowing for a comprehensive analysis of the vibrational resonances up to 4.5 THz. In that way, we illustrate the applicability of the computationally supported THz spectroscopy to detect subtle structural issues in molecular solids. While the provided structural model can be treated as a guess, the problem calls for further revision by means of high-resolution crystallography. The problem also draws a need of extending the THz experiments toward low-temperature conditions and single-crystal samples. On the other hand, the studied system emerges as a challenge for the DFT modeling, being extremely sensitive to the level of the theory used and the resulting description of the intermolecular forces. FLD form I can be, hence, considered as a testbed for the

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Computationally Assisted (Solid-State Density Functional Theory) Structural (X-ray) and Vibrational Spectroscopy (FT-IR, FT-RS, TDs-THz) Characterization of the Cardiovascular Drug Lacidipine

Abstract: International audienc

Cited by 25 publications

References 55 publications

Experimental (X-ray, ¹³C CP/MAS NMR, IR, RS, INS, THz) and Solid-State DFT Study on (1:1) Co-Crystal of Bromanilic Acid and 2,6-Dimethylpyrazine

Experimental (X-ray, ¹³C CP/MAS NMR, IR, RS, INS, THz) and Solid-State DFT Study on (1:1) Co-Crystal of Bromanilic Acid and 2,6-Dimethylpyrazine

Vibrational Dynamics of Crystalline 4-Phenylbenzaldehyde from INS Spectra and Periodic DFT Calculations

Vibrational Response of Felodipine in the THz Domain: Optical and Neutron Spectroscopy Versus Plane-Wave DFT Modeling

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Computationally Assisted (Solid-State Density Functional Theory) Structural (X-ray) and Vibrational Spectroscopy (FT-IR, FT-RS, TDs-THz) Characterization of the Cardiovascular Drug Lacidipine

Abstract: International audienc

Cited by 25 publications

References 55 publications

Experimental (X-ray, 13C CP/MAS NMR, IR, RS, INS, THz) and Solid-State DFT Study on (1:1) Co-Crystal of Bromanilic Acid and 2,6-Dimethylpyrazine

Experimental (X-ray, 13C CP/MAS NMR, IR, RS, INS, THz) and Solid-State DFT Study on (1:1) Co-Crystal of Bromanilic Acid and 2,6-Dimethylpyrazine

Vibrational Dynamics of Crystalline 4-Phenylbenzaldehyde from INS Spectra and Periodic DFT Calculations

Vibrational Response of Felodipine in the THz Domain: Optical and Neutron Spectroscopy Versus Plane-Wave DFT Modeling

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Product

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Experimental (X-ray, ¹³C CP/MAS NMR, IR, RS, INS, THz) and Solid-State DFT Study on (1:1) Co-Crystal of Bromanilic Acid and 2,6-Dimethylpyrazine

Experimental (X-ray, ¹³C CP/MAS NMR, IR, RS, INS, THz) and Solid-State DFT Study on (1:1) Co-Crystal of Bromanilic Acid and 2,6-Dimethylpyrazine