Car–Parrinello Molecular Dynamics Study of a Blue‐Shifted Intermolecular Weak‐Hydrogen‐Bond System

Rodziewicz, Paweł; Меликова, С.М.; Rutkowski, K.S.; Buda, Francesco

doi:10.1002/cphc.200400577

Cited by 14 publications

(8 citation statements)

References 43 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…8,9 However, molecular complexes of fluoroform and various other weak proton acceptors (for example N 2 , CO, or CO 2 ) show a different, more unusual behavior, namely, a considerable blue shift of the C-H stretching vibrational frequency and a decrease of the integral intensity of this band. 10 These experimental findings have been confirmed by static 10 and dynamic quantum chemical calculations, 11 and such blue-shifting H-bonds have been also observed in other fluoroform containing systems. [12][13][14] Though several and often mutually exclusive explanations have been discussed in the literature, [15][16][17][18][19][20] a clear picture of the origin of the blue-shift of the A-H vibrations in certain systems has not yet emerged.…”

Section: Introductionsupporting

confidence: 53%

“…As has been shown by previous extensive calculations, the BLYP functional and the present choice for the computational setup properly describe the unusual blue-shift effect in hydrogen-bonded molecular complexes. 11,12 The ice Ih (0001) surfaces were represented by periodically repeated slabs consisting of two ice bilayers. Only the top bilayer was allowed to relax, whereas the water molecules in the bottom bilayer were fixed at their bulk positions to mimic an infinitely extended crystal.…”

Section: Methodsmentioning

confidence: 99%

“…The binding energies of the F 3 CH monomers on the ice surface are quite high, considering the type of H-bonds which is present in this case and also in comparison to other types of complexes with fluoroform. 11,12 On the other hand, all the different possibilities to form H-bonds to the surface as shown in Fig. 2 and 3 are almost degenerate in energy.…”

Section: Optimized Structures Binding Energies and Vibrational Freque...mentioning

confidence: 98%

See 2 more Smart Citations

First-principles study of fluoroform adsorption on a hexagonal ice (0001) surface: weak hydrogen bonds—strong structural effects

Rodziewicz

Rutkowski

Meyer

2011

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

For isolated fluoroform (F(3)CH) molecules adsorbed on a hexagonal ice (0001) surface the properties of blue- and red-shifting hydrogen bonds were studied using static density functional theory (DFT) calculations and Car-Parrinello molecular dynamics (CP-MD) simulations. A systematic search by starting from many initial configurations was performed to determine the lowest-energy structures of F(3)CH on the ice surface, and for the optimized geometries the vibrational frequencies were calculated. The local minima structures are analyzed in terms of their coordination to the surface, with special focus on identifying blue-shifting hydrogen bonds via their spectroscopic signature of an increased frequency of the C-H fundamental stretching vibration. Subsequently, by CP-MD simulations the stability of the lowest-energy configurations at finite temperatures was verified and possible transformation pathways connecting the local minima structures were explored.

show abstract

Section: Introductionsupporting

confidence: 53%

Section: Methodsmentioning

confidence: 99%

Section: Optimized Structures Binding Energies and Vibrational Freque...mentioning

confidence: 98%

See 1 more Smart Citation

First-principles study of fluoroform adsorption on a hexagonal ice (0001) surface: weak hydrogen bonds—strong structural effects

Rodziewicz

Rutkowski

Meyer

2011

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

show abstract

“…Weak C-H• • • π and C-H• • • O hydrogen bonds, the crucial interactions for the microsolvation of CNTs in THF, are both known to show unusual spectroscopic properties. Our previous calculations on weakly H-bonded complexes showed that the blue-shifting phenomenon is also properly described by our DFT/PBE approach [43][44][45][46].…”

Section: Tetrahydrofuran Moleculementioning

confidence: 73%

Single-walled carbon nanotubes in tetrahydrofuran solution: microsolvation from first-principles calculations

2019

Self Cite

View full text Add to dashboard Cite

The molecular interactions between the commonly used solvent tetrahydrofuran (THF) and single-walled carbon nanotubes (SWCNT) are studied using density functional theory calculations and Car-Parrinello molecular dynamics simulations. The competitive interplay between THF-THF and THF-SWCNT interactions via C-H• • • O and C-H• • • π hydrogen bonds is analyzed in detail. The binding energies for different global and local energy minima configurations of THF monomers, dimers, trimers, and tetramers on SWCNT(10,0) were determined. The adsorbed species are analyzed in terms of their coordination to the surface via weak hydrogen bonds of the C-H• • • π type and in terms of their ability to form intermolecular C-H• • • O hydrogen bonds, which are responsible for the self-aggregation of THF molecules and a possible dimerization or tetramerization process. A special focus is put on the pseudorotation of the THF molecules at finite temperatures and on the formation of blue-shifting hydrogen bonds. Keywords Microsolvation • Tetrahydrofuran • Carbon nanotubes • DFT • CP-MD This paper belongs to the Topical Collection Tim Clark 70th Birthday Festschrift Dedicated to Tim Clark on the occasion of his 70th birthday

show abstract

“…[41][42][43][44] Recently, it has been shown that this method is also effective in studies of blue-shifted hydrogen bond formation. [45] In fact, CPMD gives a unique opportunity to study complex formation and its dynamic conformational changes practically under real conditions of hypothetical cryospectroscopic experiments in liquefied N 2 solvent (at the given temperature). The residence time and stoichiometry of the complexes can be derived in a natural way.…”

Section: Introductionmentioning

confidence: 99%

Car–Parrinello Molecular Dynamics Study of the Blue‐Shifted F₃CH⋅⋅⋅FCD₃System in Liquid N₂

et al. 2006

Self Cite

View full text Add to dashboard Cite

Fluoroform, as confirmed by both experimental and theoretical studies, can participate in improper H-bond formation, which is characterized by a noticeable increase in the fundamental stretching frequency nu(C-H) (so-called blue frequency shift), an irregular change of its integral intensity, and a C-H bond contraction. A Car-Parrinello molecular dynamics simulation was performed for a complex formed by fluoroform (F3CH) and deuterated methyl fluoride (FCD3) in liquid nitrogen. Vibrational analysis based on the Fourier transform of the dipole moment autocorrelation function reproduces the blue shift of the fundamental stretching frequency nu(C-H) and the decrease in the integral intensity. The dynamic contraction of the C-H bond is also predicted. The stoichiometry of the solvated, blue-shifted complexes and their residence times are examined.

show abstract

Car–Parrinello Molecular Dynamics Study of a Blue‐Shifted Intermolecular Weak‐Hydrogen‐Bond System

Cited by 14 publications

References 43 publications

First-principles study of fluoroform adsorption on a hexagonal ice (0001) surface: weak hydrogen bonds—strong structural effects

First-principles study of fluoroform adsorption on a hexagonal ice (0001) surface: weak hydrogen bonds—strong structural effects

Single-walled carbon nanotubes in tetrahydrofuran solution: microsolvation from first-principles calculations

Car–Parrinello Molecular Dynamics Study of the Blue‐Shifted F₃CH⋅⋅⋅FCD₃System in Liquid N₂

Contact Info

Product

Resources

About

Car–Parrinello Molecular Dynamics Study of a Blue‐Shifted Intermolecular Weak‐Hydrogen‐Bond System

Cited by 14 publications

References 43 publications

First-principles study of fluoroform adsorption on a hexagonal ice (0001) surface: weak hydrogen bonds—strong structural effects

First-principles study of fluoroform adsorption on a hexagonal ice (0001) surface: weak hydrogen bonds—strong structural effects

Single-walled carbon nanotubes in tetrahydrofuran solution: microsolvation from first-principles calculations

Car–Parrinello Molecular Dynamics Study of the Blue‐Shifted F3CH⋅⋅⋅FCD3System in Liquid N2

Contact Info

Product

Resources

About

Car–Parrinello Molecular Dynamics Study of the Blue‐Shifted F₃CH⋅⋅⋅FCD₃System in Liquid N₂