Simulation by molecular dynamics of poly(1,4-trans-butadiene) as an inclusion complex in the channel of crystalline perhydrotriphenylene

Dodge, Robert; Mattice, Wayne L.

doi:10.1021/ma00010a011

Cited by 39 publications

(29 citation statements)

References 7 publications

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“…The results obtained with PTBD in PHTP show that there are rapid conformational transitions between anticlinal states and large fluctuations in the dihedral angles within an anticlinal state at CH-CH 2 bonds. These internal motions rapidly randomize the angular distribution of a C-H bond vector about the axis of the channel [65,66]. This rapid randomization has been demonstrated experimentally by deuterium NMR of PTBD with deuterated methylene groups [54].…”

Section: Molecular Modeling Using the Rotational Isomeric State Modelmentioning

confidence: 85%

“…Recently, molecular dynamics simulations have been used to study the conformations and mobility of PTBD and PTIP in the channels of crystalline PHTP and PE in the channels of urea ICs by Dodge, Mattice, and Zhan [65][66][67][68]. They used the crystal structure parameters [12], known from x-ray structure analysis, to set up each host clathrate molecule position, and then they made a crystalline channel lattice in which they placed a polymer chain fragment.…”

Section: Molecular Modeling Using the Rotational Isomeric State Modelmentioning

confidence: 99%

See 1 more Smart Citation

Polymer Inclusion Compounds

Huang¹,

Tonelli²

1998

Journal of Macromolecular Science, Part C: Polymer Reviews

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Section: Molecular Modeling Using the Rotational Isomeric State Modelmentioning

confidence: 85%

Section: Molecular Modeling Using the Rotational Isomeric State Modelmentioning

confidence: 99%

Polymer Inclusion Compounds

Huang¹,

Tonelli²

1998

Journal of Macromolecular Science, Part C: Polymer Reviews

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“…The potential energy of the system, E, was calculated as Parameters for bond bending and torsion in the Dreiding force field were modified particularly for use to polybutadiene, as described in a previous work. 18 A polymer chain with a degree of polymerization of 99 was generated with all CH==CH double bonds in the cis conformation, corresponding to pure cis-polybutadiene ( Figure 1). As mentioned above, all hydrogen atoms were explicitly taken into consideration.…”

Section: Structure Modelmentioning

confidence: 99%

Atom-based modeling of amorphous 1,4-cis-polybutadiene

Yong¹,

Mattice²

1992

Macromolecules

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The structure of amorphous 1,4-cis-polybutadiene is simulated with molecular mechanics and molecular dynamics subjected to periodic boundary conditions. All hydrogen atoms are explicitly taken into account. By means of the relaxation strategy which has been developed in this work, the low-energy states of relatively large systems can be reached within an acceptable computational time. With the five simulated structures, the distribution of bond angles, distribution of dihedral angles, and correlated distribution of pairs of neighbor dihedral angles, as well as cohesive energy, solubility parameter, and atom pair radial distribution functions, are evaluated and discussed.

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“…Recent investigations of a,o-alkyl-oligothiophenes in tris(o-phenylenedioxy)spirocyclotriphosphazene (TPP) have shown that the terminal alkane chains act as hinges around which the central bithiophene moiety rotates in a quasi-free way. 34 Molecular dynamics (MD) simulations and quantum chemical calculations [44][45][46][47][48][49] provided a detailed insight into the mechanisms of molecular motions and showed that the roles of the organic ''zeolites'', such as PHTP and TPP, are completely different from that of real zeolites. Whereas zeolites form fairly rigid channels, the shape and size of the PHTP channels are variable to a certain degree.…”

Section: Introductionmentioning

confidence: 99%

Dynamics of guest molecules in PHTP inclusion compounds as probed by solid-state NMR and fluorescence spectroscopy

Srinivasan

Villanueva-Garibay

Müller

et al. 2009

Phys. Chem. Chem. Phys.

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Partially deuterated 1,4-distyrylbenzene () is included into the pseudohexagonal nanochannels of perhydrotriphenylene (PHTP). The overall and intramolecular mobility of is investigated over a wide temperature range by (13)C, (2)H NMR as well as fluorescence spectroscopy. Simulations of the (2)H NMR spectral shapes reveal an overall wobble motion of in the channels with an amplitude of about 4 degrees at T = 220 K and 10 degrees at T = 410 K. Above T = 320 K the wobble motion is superimposed by localized 180 degrees flips of the terminal phenyl rings with a frequency of 10(6) Hz at T = 340 K. The activation energies of both types of motions are around 40 kJ mol(-1) which imply a strong sterical hindrance by the surrounding PHTP channels. The experimental vibrational structure of the fluorescence excitation spectra of is analyzed in terms of small amplitude ring torsional motions, which provide information about the spatial constraints on by the surrounding PHTP host matrix. Combining the results from NMR and fluorescence spectroscopy as well as of time-dependent density functional calculations yields the complete potential surfaces of the phenyl ring torsions. These results, which suggest that intramolecular mobility of is only reduced but not completely suppressed by the matrix, are corroborated by MD simulations. Unrealistically high potential barriers for phenyl ring flips are obtained from MD simulations using rigid PHTP matrices which demonstrate the importance of large amplitude motions of the PHTP host lattice for the mobility of the guest molecules.

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Simulation by molecular dynamics of poly(1,4-trans-butadiene) as an inclusion complex in the channel of crystalline perhydrotriphenylene

Cited by 39 publications

References 7 publications

Polymer Inclusion Compounds

Polymer Inclusion Compounds

Atom-based modeling of amorphous 1,4-cis-polybutadiene

Dynamics of guest molecules in PHTP inclusion compounds as probed by solid-state NMR and fluorescence spectroscopy

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