Benzene Trimer Research Articles

Assessment of fine and coarse tyre wear particles along a highway stormwater system and in receiving waters: Occurrence and transport

Tyre wear has been identified as a major road-related pollutant source, with road runoff transporting tyre wear particles (TWP) to adjacent soil, watercourses, or further through stormwater systems. The aim of this study was to investigate the occurrence and transport of TWP along a stormwater system. Water and sediment have been sampled at selected points (road runoff, gully pots, wells, outlet to a ditch, and stream) through a stormwater system situated along a highway in Sweden during November and December 2022, and March 2023. As there is limited data on the size distribution of TWP in different environmental media, especially in the size fraction <20 μm, the samples were fractioned into a fine (1.6–20 μm) and a coarse (1.6–500 μm) size fraction. The samples were analysed using a combination of marker compounds (benzene, α-methylstyrene, ethylstyrene, and butadiene trimer) for styrene-butadiene rubbers with PYR-GC/MS from which TWP concentration was calculated. Suspended solids were analysed in the water samples, and organic content was analysed in the sediment samples. TWP was found at nearly all locations, with concentrations up to 17 mg/L in the water samples and up to 40 mg/g in the sediment samples. In the sediment samples, TWP in the size fraction 1.6–20 μm represented a significant proportion (20–60%). Correlations were found between TWP concentration and suspended solids in the water samples (r = 0.87) and organic content in the sediment samples (r = 0.72). The results presented in this study demonstrate that TWP can be transported to the surrounding environment through road runoff, with limited retention in the studied stormwater system.

Thermal curing mechanisms and cross-linking network structure of a novel silicon-containing arylacetylene resin with 2,7-diethynylnaphthalene unit

Silicon-containing arylacetylene resin and its composites have attracted great interest as emerging heat-resistant materials, but their curing mechanisms and products are still elusive. In this work, the influences of the terminal and inner acetylenes on the curing mechanisms of silicon-containing arylacetylene resin with 2,7-diethynylnaphthalene were first identified by density functional theory. Two reaction pathways were proposed and their products include polyenes, anthracene dimers, and benzene trimers. To gain a distinct observation of the cross-linking process, molecular dynamics simulations were used to construct a cross-linking polymerization model. The effects of the temperature on the cured structure were investigated by analyzing the characteristics of the cross-linked network. As expected, higher curing temperature will make the larger proportion of polyene chain and aromatic ring in the terminal alkyne−terminal alkyne route, meanwhile, for the inner alkyne−inner alkyne route, the short chains and a small amount of aromatic rings are major productions. Overall, our cross-linking method may provide an unique guidance for studying the cured structure of other thermosetting resins.

Triple ionization and fragmentation of benzene trimers following ultrafast intermolecular Coulombic decay

Intermolecular interactions involving aromatic rings are ubiquitous in biochemistry and they govern the properties of many organic materials. Nevertheless, our understanding of the structures and dynamics of aromatic clusters remains incomplete, in particular for systems beyond the dimers, despite their high presence in many macromolecular systems such as DNA and proteins. Here, we study the fragmentation dynamics of benzene trimer that represents a prototype of higher-order aromatic clusters. The trimers are initially ionized by electron-collision with the creation of a deep-lying carbon 2s−1 state or one outer-valence and one inner-valence vacancies at two separate molecules. The system can thus relax via ultrafast intermolecular decay mechanisms, leading to the formation of C{}_{6}{{{{{{{{{rm{H}}}}}}}}}_{6}}^{+}cdotC{}_{6}{{{{{{{{{rm{H}}}}}}}}}_{6}}^{+}cdotC{}_{6}{{{{{{{{{rm{H}}}}}}}}}_{6}}^{+} trications and followed by a concerted three-body Coulomb explosion. Triple-coincidence ion momentum spectroscopy, accompanied by ab-initio calculations and further supported by strong-field laser experiments, allows us to elucidate the details on the fragmentation dynamics of benzene trimers.

DFT studies of aggregation induced energy splitting and excitonic diversification in benzene and anthracene multimers

Aggregation of organic molecules greatly impacts the performance of organic electronic devices, yet understanding of the changes induced by the aggregation has not been well understood. In this work, we investigated molecular multimers of benzene and anthracene with varying numbers of molecules utilizing density functional theory calculations with three dispersion functionals. The DFT results indicate that B3LYP-D3 is a good functional in describing the benzene and anthracene multimers. The TDDFT results show that UV–Vis spectra are significantly different in benzene trimers and beyond in comparison to the dimer, while the redshift in absorption increases with the number of molecules in anthracene multimers. The normalized general variance analysis of orbitals illustrates that hole delocalization reaches maximum in hexamers for the aggregates. In contrast, electron delocalization remains nearly unchanged from dimer to octamer in benzene aggregates but increases monotonically in anthracene aggregates. These results suggest that aggregation assists exciton dissociation.

Dynamical Behavior of Aromatic Trimer Complexes in Unimolecular Dissociation Reaction at High Temperatures. Case Studies on C6H6-C6F6-C6H6 and C6H6 Trimer Complexes.

The intramolecular vibrational energy redistribution (IVR) dynamics during unimolecular dissociation of aromatic trimers at high temperatures is the primary interest of this study. Chemical dynamics simulations are performed for the unimolecular dissociation of benzene-hexafluorobenzene-benzene (Bz-HFB-Bz) and benzene trimer (Bz-trimer) complexes at a temperature range of 1000-2000 K. Partial dissociation of both the complexes is observed, which leads to a dimer and a monomer in the dynamics. However, the probability of such dissociation was found much lower in the case of the Bz-trimer, which further decreases with the increase of temperature. The rate of partial dissociation of Bz-HFB-Bz is faster at 1500, 1800, and 2000 K, whereas the rate of complete dissociation of the Bz-trimer is significantly faster than Bz-HFB-Bz at all temperatures. This is just the opposite of the corresponding dimer's dissociation, where benzene-hexafluorobenzene (Bz-HFB) dissociates at a faster rate than the benzene dimer (Bz-dimer). Thus, the dissociation dynamics of the trimer is different than that of the dimer. Simulations with excited intramolecular and intermolecular modes of the trimer complexes reveal that energy flows from intermolecular to intramolecular modes of Bz-HFB-Bz more freely than the Bz-trimer, and the dissociation process becomes slower for the former. Calculated activation energies for both types of dynamics are much lower than the corresponding binding energies, which may be due to the anharmonicity. The Arrhenius equation with an anharmonic correction factor is considered to recalculate the activation energy and pre-exponential factor.

Quantum Chemical Exploration of Intermolecular Reactions of Acetylene.

Quantum chemical explorations of potential energy surfaces showed that acetylene produces various products starting from molecular arrays in short distances of 1.3-2.5 Å. Arrays of (C2 H2 )2 gave cyclobutadiene, tetrahedrane, and acetylene dimers. Arrays of (C2 H2 )3 gave benzene, prismane, benzvalene, Dewar benzene, and acetylene trimers. Arrays of (C2 H2 )4 gave cubane, cyclooctatetranene, and acetylene tetramers. Different forms of initial arrays yielded different sets of products; a parallel array of two monomers gave cyclobutadiene, whereas a cross array gave tetrahedrane. Initial molecular arrays with unusually close contacts were estimated to require local forces of 1-9 × 10-8 N. © 2019 Wiley Periodicals, Inc.

Automatic Conformational Search of Transition States for Catalytic Reactions Using Genetic Algorithm.

With the ever-increasing computational power available to carry out expensive quantum mechanics calculations and the ever-increasing complexity of transition state conformational search problems, a program performing an automatic conformational search will be a valuable tool for computational and experimental chemists. In this manuscript, we report the development and testing of a computational program (QMTSDock) that can automatically search the conformational space of a noncovalent interaction catalyzed transition state or molecular clusters, using quantum mechanics (QM) methods. This program adopts a docking approach using the genetic algorithm (GA). The program allows users to choose the QM method and permits the use of multiple catalysts. New interesting cluster structures were obtained for the GA studies of water heptamer and benzene trimer, while new mechanistic insights have been gained from the GA studies of asymmetric Strecker reaction and asymmetric methanolysis of mesocyclic anhydride reaction.

Water-accelerated \u03c0-Stacking Reaction in Benzene Cluster Cation

Single molecule electron devices (SMEDs) have been widely studied through both experiments and theoretical calculations because they exhibit certain specific properties that general macromolecules do not possess. In actual SMED systems, a residual water molecule strongly affects the electronic properties of the SMED, even if only one water molecule is present. However, information about the effect of H2O molecules on the electronic properties of SMEDs is quite limited. In the present study, the effect of H2O on the ON-OFF switching property of benzene-based molecular devices was investigated by means of a direct ab initio molecular dynamics (AIMD) method. T- and H-shaped benzene dimers and trimers were examined as molecular devices. The present calculations showed that a H2O molecule accelerates the π-stacking formation in benzene molecular electronic systems. The times of stacking formation in a benzene dimer cation (n = 2) were calculated to be 460 fs (H2O) and 947 fs (no-H2O), while those in a trimer cation (n = 3) were 551 fs (H2O) and 1019 fs (no-H2O) as an average of the reaction time. This tendency was not dependent on the levels of theory used. Thus, H2O produced positive effects in benzene-based molecular electronics. The mechanism of π-stacking was discussed based on the theoretical results.

Experimental and theoretical investigation of intramolecular cooperativity in cyclic benzene trimer motif.

A series of new symmetrical tripodal molecules 1a–4b with a central benzene scaffold substituted with methyl/ethyl groups and three benzimidazolyl units having a bithiophene/biphenyl/5-alkylthiophene motif at the 2-position via a –CH2– unit were synthesized and characterized by elemental analysis, HR-MS, and NMR spectroscopy. NMR spectral data reveal that all molecules adopt a cyclic benzene trimer (CBT) using three benzimidazolyl units. Intramolecular cooperative edge-to-face C–H⋯π interactions stabilize the CBT motif in solution and are strong in ethyl substituted molecules (1b–4b) compared to methyl substituted (1a–4a) ones. However, the strength of the CBT unit in the tripodal molecule is independent of the length of the substituent at the 2-position of the benzimidazolyl unit. The relative 1H NMR chemical shift calculated at the MPW1PW91/6-311+G(d,p) level of theory corroborates the experimental values, and the calculations predict the distribution of the structures into syn isomers. The relative change in the NMR chemical shift is justified by the relative change in the magnitude of the (3,+3) critical point (CP) in the molecular electrostatic potential (MESP) topography. Also, a linear correlation of the intramolecular C–H⋯π interactions evaluated at M062X/6-311+G(d,p) with the relative NMR chemical shift suggest the latter as a measure of intramolecular cooperativity.

Timescale of π‐Stacking Formation in a Benzene Trimer Cation Formed by Ionization of the Parent Neutral Trimer: A Direct Ab Initio Molecular Dynamics Study

AbstractThe π‐stacking interaction plays a crucial role in structural arrangements and molecular assemblies in several molecular systems. In the present study, π‐stacking formation in the benzene trimer cation, (Bz)3+, following ionization of the parent neutral benzene trimer, (Bz)3, was investigated using direct ab initio molecular dynamics to elucidate the timescale of π‐stacking formation and reaction mechanism in the ionized state. Cyclic (Bz)3 was chosen as the benzene cluster. After ionizing (Bz)3, the structure drastically changed to a double π‐stacking form. The (Bz)3+ product vibrated between two structural forms, (Bz‐Bzc)+—Bz ↔ Bz—(Bzc‐Bz)+, where Bzc is a benzene molecule located in the central position of (Bz)3+ and (Bzc‐Bz)+ represents a dimer core composed of the benzene dimer cation. The timescale of π‐stacking formation was calculated as 300–380 fs. The absorption spectrum of (Bz)3+ was blue‐shifted as a function of time. We discuss the reaction mechanism based on the theoretical results.

Density-functional approach to the three-body dispersion interaction based on the exchange dipole moment.

We implement and compute the density functional nonadditive three-body dispersion interaction using a combination of Tang-Karplus formalism and the exchange-dipole moment model of Becke and Johnson. The computation of the C9 dispersion coefficients is done in a non-empirical fashion. The obtained C9 values of a series of noble atom triplets agree well with highly accurate values in the literature. We also calculate the C9 values for a series of benzene trimers and find a good agreement with high-level ab initio values reported recently in the literature. For the question of damping of the three-body dispersion at short distances, we propose two damping schemes and optimize them based on the benzene trimers data, and the fitted analytic potentials of He3 and Ar3 trimers fitted to the results of high-level wavefunction theories available from the literature. Both damping schemes respond well to the optimization of two parameters.

What Is the Structure of the Naphthalene-Benzene Heterodimer Radical Cation? Binding Energy, Charge Delocalization, and Unexpected Charge-Transfer Interaction in Stacked Dimer and Trimer Radical Cations.

The binding energy of the naphthalene(+•)(benzene) heterodimer cation has been determined to be 7.9 ± 1 kcal/mol for C10H8(+•)(C6H6) and 8.1 ± 1 kcal/mol for C10H8(+•)(C6D6) by equilibrium thermochemical measurements using the mass-selected drift cell technique. A second benzene molecule binds to the C10H8(+•)(C6D6) dimer with essentially the same energy (8.4 ± 1 kcal/mol), suggesting that the two benzene molecules are stacked on opposite sides of the naphthalene cation in the (C6D6)C10H8(+•)(C6D6) heterotrimer. The lowest-energy isomers of the C10H8(+•)(C6D6) and (C6D6)C10H8(+•)(C6D6) dimer and trimer calculated using the M11/cc-pVTZ method have parallel stacked structures with enthalpies of binding (-ΔH°) of 8.4 and 9.0 kcal/mol, respectively, in excellent agreement with the experimental values. The stacked face-to-face class of isomers is calculated to have substantial charge-transfer stabilization of about 45% of the total interaction energy despite the large difference between the ionization energies of benzene and naphthalene. Similarly, significant delocalization of the positive charge is found among all three fragments of the (C6D6)C10H8(+•)(C6D6) heterotrimer, thus leaving only 46% of the total charge on the central naphthalene moiety. This unexpectedly high charge-transfer component results in activating two benzene molecules in the naphthalene(+•)(benzene)2 heterotrimer cation to associate with a third benzene molecule at 219 K to form a benzene trimer cation and a neutral naphthalene molecule. The global minimum of the C10H8(+•)(C6H6)2 heterotrimer is found to be the one where the naphthalene cation is sandwiched between two benzene molecules. It is remarkable, and rather unusual, that the binding energy of the second benzene molecule is essentially the same as that of the first. This is attributed to the enhanced charge-transfer interaction in the stacked trimer radical cation.

Density-fitted singles and doubles coupled cluster on graphics processing units

We adapt an algorithm for singles and doubles coupled cluster (CCSD) that uses density fitting or Cholesky decomposition (CD) in the construction and contraction of all electron repulsion integrals (ERIs) for use on heterogeneous compute nodes consisting of a multicore central processing unit (CPU) and at least one graphics processing unit (GPU). The use of approximate three-index ERIs ameliorates two of the major difficulties in designing scientific algorithms for GPUs: (1) the extremely limited global memory on the devices and (2) the overhead associated with data motion across the bus. For the benzene trimer described by an aug-cc-pVDZ basis set, the use of a single NVIDIA Tesla C2070 (Fermi) GPU accelerates a CD-CCSD computation by a factor of 2.1, relative to the multicore CPU-only algorithm that uses six highly efficient Intel Core i7-3930K CPU cores. The use of two Fermi GPUs provides an acceleration of 2.89, which is comparable to that observed when using a single NVIDIA Kepler K20c GPU (2.73).

Dimers and trimers of polycyclic aromatic hydrocarbons as models of graphene bilayers and trilayers: enhanced electron density at the edges

Structures of dimers and trimers of polycyclic aromatic hydrocarbons (PAHs) having zig-zag edges, and continuous electron density and molecular electrostatic potential (MEP) distributions in these systems were studied in gas phase. Dimers of benzene and naphthalene for which high-accuracy results are available were used to test the reliability of four different functionals of density functional theory in combination with the 6-31G(d,p) basis set. The dispersion-corrected WB97XD functional was found to be distinctly superior to the other three functionals used and was employed to study PAH dimers and trimers. Electronic structures and geometries of dimers of a four benzene ring and a nine benzene ring systems and trimers of the four benzene ring system were investigated. The dimers and trimers of PAHs were found to be of parallel-displaced type, as observed experimentally for graphene. The enhanced electron density edge effect found in the PAH monomers earlier is found to exist in the dimers and trimers also.

Double π–π stacking dynamics of benzene trimer cation: direct ab initio molecular dynamics (AIMD) study

Mechanism of π–π double stacking process of benzene trimer cation has been investigated by means of direct ab initio molecular dynamics method. It was found that H-shaped form of neutral benzene trimer is drastically changed to the π–π double stacking form composed of benzene trimer cation following the ionization. Absorption spectrum of charge resonance band of (Bz) 3 + was gradually blueshifted as a function of time. Time scale of the double stacking process (the formation of trimer cation from the H-shaped form) was calculated to be 0.7–1.5 ps, which is comparable to that of dimer cation formation. After the ionization of benzene trimer, (Bz)(Bz)c(Bz′), the hole is distributed around three benzene molecules with a branching ratio of (Bz)+0.3(Bz)c+0.4(Bz′)+0.3, and the structure of (Bz)c+ was rapidly deformed due to the Jahn–Teller effect. Next, the molecular rotation of central benzene (Bz)c+ occurred gradually. Immediately, both benzene molecules in the wing positions were also rotated synchronicity. Finally, the π–π double stacking form composed of benzene trimer cation was formed. The formation mechanism of benzene trimer cation was discussed on the basis of theoretical results.

Accuracy and Efficiency of Coupled-Cluster Theory Using Density Fitting/Cholesky Decomposition, Frozen Natural Orbitals, and a t1-Transformed Hamiltonian.

We present an algorithm for coupled-cluster through perturbative triples [CCSD(T)] based on a t1-dressed Hamiltonian and the use of density fitting (DF) or Cholesky decomposition (CD) approximations for the construction and contraction of all electron repulsion integrals (ERIs). An efficient implementation of this algorithm is then used to explore whether preoptimized density fitting basis sets [specifically, the (aug-)cc-pVXZ-RI series designed for DF-MP2 computations] are suitable for DF-CCSD(T) computations and how they compare to the CD representation of the integrals. The code is also used to systematically explore the accuracy and efficiency of DF/CD combined with frozen natural orbitals (FNOs) to reduce computational costs. The mean absolute errors due to DF/CD in the CCSD(T)/aug-cc-pVDZ interaction energies of 11 van der Waals dimers are only 0.001 kcal mol(-1) for the preoptimized RI basis set and only 0.002 and 0.001 kcal mol(-1) for CD with cutoffs of 10(-4) and 10(-5), respectively. The very similar performance of the aug-cc-pVDZ-RI auxiliary set is a bit surprising considering that the numbers of CD vectors using these thresholds are, on average, 28% and 73% larger than the dimension of the RI set. When FNOs are coupled with DF/CD, the DF/CD error is roughly an order of magnitude less than the FNO truncation error (at a conservative FNO occupation cutoff of 10(-5)). Utilizing t1-dressed three-index integrals, which remove the explicit dependence of the doubles residual equations on the t1-amplitudes, results in a moderate performance acceleration for the CCSD portion of the algorithm. Moreover, the t1-dressing results in a simpler code which will be more amenable to parallelization. Utilizing both CD and FNO techniques, we observe a speedup of four times for the evaluation of the three-body contribution to the interaction energy for the benzene trimer described by an aug-cc-pVDZ basis set; the error incurred by the CD and FNO approximations in the three-body contribution is only 0.002 kcal mol(-1).

Vibrational Spectroscopy and Theory of the Protonated Benzene Dimer and Trimer

Protonated benzene cluster ions, H(C(6)H(6))(2)(+) and H(C(6)H(6))(3)(+), are produced in a pulsed electrical discharge source coupled to a supersonic expansion. Mass-selected complexes are investigated with infrared photodissociation spectroscopy in the 1000-3200 cm(-1) region using the method of argon tagging. The IR spectra of H(C(6)H(6))(2)(+)-Ar and H(C(6)H(6))(3)(+)-Ar contain broad bands in the high frequency region resulting from CH-π hydrogen bonds. Sharp peaks are observed in the fingerprint region arising from the ring modes of both the C(6)H(7)(+) and C(6)H(6) moieties. M06-2X calculations have been performed to investigate the structures and vibrational spectra of energetically low-lying configurations of these complexes. H(C(6)H(6))(2)(+) is predicted to have three nearly isoenergetic conformers: the parallel displaced (PD), T-shaped (TS), and canted (C) structures [Jaeger, H. M.; Schaefer, H. F.; Hohenstein, E. G.; Sherrill, C. D. Comput. Theor. Chem. 2011, 973, 47-52]. A comparison of the experimental dimer spectrum with those predicted for the three isomers suggests an average structure between the TS and PD conformers, which is consistent with the low energy barrier predicted to separate these two structures. No evidence is found for the C dimer even though it lies only 1.2 kcal/mol above the PD dimer. Although the trimer is also computed to have many low lying isomers, the IR spectrum limits the possible species present.

Vibrational energy relaxation of benzene dimer and trimer in the CH stretching region studied by picosecond time-resolved IR-UV pump-probe spectroscopy

Vibrational energy relaxation (VER) of the Fermi polyads in the CH stretching vibration of the benzene dimer (Bz(2)) and trimer (Bz(3)) has been investigated by picosecond (ps) time-resolved IR-UV pump-probe spectroscopy in a supersonic beam. The vibrational bands in the 3000-3100 cm(-1) region were excited by a ps IR pulse and the time evolutions at the pumped and redistributed (bath) levels were probed by resonance enhanced multiphoton ionization with a ps UV pulse. For Bz(2), a site-selective excitation in the T-shaped structure was achieved by using the isotope-substituted heterodimer hd, where h = C(6)H(6) and d = C(6)D(6), and its result was compared with that of hh homodimer. In the hd heterodimer, the two isomers, h(stem)d(top) and h(top)d(stem), show remarkable site-dependence of the lifetime of intracluster vibrational energy redistribution (IVR); the lifetime of the Stem site [h(stem)d(top), 140-170 ps] is ~2.5 times shorter than that of the Top site [h(top)d(stem), 370-400 ps]. In the transient UV spectra, a broad electronic transition due to the bath modes emerges and gradually decays with a nanosecond time scale. The broad transition shows different time profile depending on UV frequency monitored. These time profiles are described by a three-step VER model involving IVR and vibrational predissociation: initial → bath1(intramolecular) → bath2(intermolecular) → fragments. This model also describes well the observed time profile of the Bz fragment. The hh homodimer shows the stepwise VER process with time constants similar to those of the hd dimer, suggesting that the excitation-exchange coupling of the vibrations between the two sites is very weak. Bz(3) also exhibited the stepwise VER process, though each step is faster than Bz(2).

Theoretical ab initio study of substituted benzene trimer: Interplay between hydrogen bonding and π–π interactions

The interplay between two important noncovalent interactions involving aromatic rings is studied by means of ab initio calculations (RI-MP2/aug-cc-pVTZ//RI-MP2/aug-cc-pVDZ level of theory). We demonstrate that synergetic effects are present in complexes where hydrogen bonding interactions and π–π interactions coexist and that these effects are transmitted through the space to a third aromatic ring. The π–π interaction is influenced by the presence/absence of hydrogen bonding interactions that are established in a third π-system far from the stacking interaction. These synergetic effects have been studied using energetic and geometric criteria and the Bader’s theory of “atoms in molecules”.

Thermal decomposition of expanded polystyrene in a pebble bed reactor to get higher liquid fraction yield at low temperatures

Expanded polystyrene is one of the polymers produced in large quantities due to its versatile application in different fields. This polymer is one of the most intractable components in municipal solid waste. Disposal of polymeric material by pyrolysis or catalytic cracking yields valuable hydrocarbon fuels or monomers. Literature reports different types of reactors and arrangements that have uniform temperatures during pyrolysis and catalytic cracking. The present study focuses on reducing the temperature to maximize the quantity of styrene monomer in the liquid product. A bench scale reactor has been developed to recover the styrene monomer and other valuable chemicals. Experiments were carried under partial oxidation and vacuum conditions in the temperature range of 300-500 degrees C. In the pyrolysis optimization studies, the best atmospheric condition was determined to be vacuum, the pyrolysis temperature should be 500 degrees C, yield of liquid product obtained was 91.7% and yield of styrene obtained was 85.5%. In the characterization studies, distillation and IR spectroscopy experiments were carried out. The remaining of the liquid product comprises of benzene, ethyl benzene, and styrene dimers and trimers.