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Simulating molecular structures and dynamic behaviors presents critical insights into the microscopic mechanisms governing variations in charge transport properties. In this work, molecular dynamics (MD) simulations integrated with the Compass II force field and molecular modeling (including geometry optimization, annealing, and dynamic equilibration) are conducted to systematically analyze intermolecular interaction energy, free volume distribution, electronic density of states (DOS), charge differential density, and trap energy levels. aiming to unravel the regulatory role of hydrogen bonds in the structural evolution and charge transport dynamics of polypropylene (PP)/polyvinylidene fluoride (PVDF) composite systems. A quantitative framework is further established to correlate hydrogen bond density with key material performance metrics, such as free volume fraction, bandgap energy, and trap energy depth, thereby elucidating the hydrogen bond-mediated modulation of molecular architecture and charge transport behavior in PP/PVDF composites. Simulation results reveal a pronounced dependence of hydrogen bond formation on maleic acid (MA) grafting content. When the mass fraction of MA is 36.22%, the number of hydrogen bonds reaches a maximum value of 20, the intermolecular interaction energy increases to 2171.63 kcal·mol–1, and the free volume fraction reaches a minimum value of 16.03%. At this point, the internal structure of the molecule is most compact. When the mass fraction of MA increases to 52.97%, the band gap of the composite material reaches a minimum value of 3.13 eV, and the depth of the trap energy levels also reaches a maximum value of 3.06 eV. Spatial charge differential density analysis demonstrates that the enhanced electron density is localized near hydrogen-bonded region, thus suppressing electron escape probability by over 40% compared with the scenario in the non-bonded domains. All of the findings highlight a dual mechanism: hydrogen bonds not only reconfigure the molecular topology but also reshape the localized charge distribution, directly suppressing the carrier mobility and changing the charge transport pathways. These findings also establish a robust structure-property relationship, showing that hydrogen bond engineering serves as a pivotal strategy to tailor dielectric performance in polymer composites. By optimizing hydrogen bond density, the trade-off between structural compactness and electronic confinement can be strategically balanced, thus enabling the designing of PP-based dielectrics with low carbon footprints and superior insulating properties. This mechanistic understanding provides actionable guidelines for advancing high-performance insulating materials in energy storage systems, aerospace components, and next-generation electrical devices, where precise control over charge transport is paramount.
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Keywords:
- polypropylene /
- hydrogen bond /
- molecular dynamics /
- charge transport
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] [37] -
Epotential Function form Parameters and units Ebond $ {E_{{\text{bond}}}} = \displaystyle\sum\limits_{{\text{bonds}}} {{k_b}{{(r - {r_0})}^2} + k_b^{(3)}{{(r - {r_0})}^3} + k_b^{(4)}{{(r - {r_0})}^4}} $ kb/(kcal·mol–1·Å–2); r, r0/Å Eangle $ {E_{{\text{angle}}}} = \displaystyle\sum\limits_{{\text{angles}}} {{k_\theta }{{(\theta - {\theta _0})}^2} + k_\theta ^{(3)}{{(\theta - {\theta _0})}^3} + k_\theta ^{(4)}{{(\theta - {\theta _0})}^4}} $ kθ/(kcal·mol–1); θ, θ0/(°) Etorsion $ {E_{{\text{torsion}}}} = \displaystyle\sum\limits_{{\text{torsions}}} {{k_\varphi }(1 + \cos (n} \varphi - {\varphi _0})) $ kφ/(kcal·mol–1); φ, φ0/(°) Eout-of-plane $ {E_{{\text{out-of-plane}}}} = \displaystyle\sum\limits_{{\text{out-of-plane}}} {{k_\omega }{\omega ^2}} $ kω/(kcal·mol–1); ω/(°) Evdw $ {E_{{\text{vdW}}}} = \displaystyle\sum\limits_{i, j} {4\varepsilon \left[ {{{\left( {\frac{\sigma }{{{r_{ij}}}}} \right)}^{12}} - {{\left( {\frac{\sigma }{{{r_{ij}}}}} \right)}^6}} \right]} $ Ε/eV; σ/Å; rij/Å Eelectrostatic $ {E_{{\text{electrostatic}}}} = \displaystyle\sum\limits_{i, j} {\frac{{{q_i}{q_j}}}{{4\pi {\varepsilon _0}{r_{ij}}}}} $ qi, qj/e; rij/Å 
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试样编号
PP-g-MA/%PVDF/% MA PP 1# 0 77.94 22.26 2# 2.74 75.52 21.74 3# 5.33 73.41 21.26 4# 10.13 69.57 20.30 5# 14.50 65.94 19.56 6# 18.47 62.83 18.70 7# 22.05 59.84 18.11 8# 36.22 48.51 15.27 9# 52.97 35.34 11.69
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试样
编号平衡
时间/ps波动/% 温度 Epotential Ekinetic Enon-bond Etotal 1# 58.93 3.25 1.56 3.85 4.52 4.11 2# 74.68 2.89 2.56 4.26 1.57 2.10 3# 25.95 4.56 4.56 3.73 2.94 1.61 4# 78.59 1.12 2.76 1.52 4.51 1.52 5# 85.45 2.59 3.81 1.14 1.52 3.20 6# 36.58 3.58 4.19 2.81 2.73 2.17 7# 57.58 1.56 1.25 4.20 2.85 3.96 8# 85.42 3.20 2.48 1.52 4.22 2.57 9# 54.20 2.74 4.21 1.23 2.52 1.85
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Enon-bond/(kcal·mol–1)
Ediagonal/(kcal·mol–1)Einteraction
/(kcal·mol–1)Etotal
/(kcal·mol–1)Evdw Eelectrostatic Ebond Eangle Etorsion 1# 84.65 853.99 214.04 371.93 –721.02 53.49 552.18 2# 85.17 906.80 215.48 398.77 –728.18 63.88 601.15 3# 86.71 977.26 217.09 412.65 –751.63 75.86 654.46 4# 97.89 1083.01 218.45 448.12 –753.56 85.58 723.28 5# 110.28 1205.79 242.31 453.70 –770.93 88.09 828.37 6# 110.97 1332.96 264.16 536.79 –787.47 89.02 898.72 7# 122.93 1462.88 268.80 547.69 –792.07 108.50 1002.49 8# 132.42 2094.95 309.91 689.15 –858.76 127.05 1413.73 9# 55.29 3377.36 402.88 1026.23 –1028.7 74.86 2171.63
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[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] [37]
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