Theoretical study of hydrogen abstraction by HO2 radicals from primary straight chain amines CnH2n+1-NH2 (n = 1-4).

Hydrogen abstraction reactions by HO2 radicals from four primary amines including methylamine (MA), ethylamine (EA), n-propylamine (PA), and n-butylamine (BA), are investigated and the effect of the functional group on rate constants at different reaction sites is examined. A hybrid functional BH&HLYP coupled with cc-pVTZ as the basis set is utilized to determine geometry optimizations, frequencies, and connections between transition states and corresponding local minima. By comparing the reaction energies obtained by several density functional theory methods to those obtained using the gold-standard CCSD(T)/CBS(T-Q) method, the M08-HX/maug-cc-pVTZ combination is identified as the best suitable method with a mean unsigned deviation of 0.81 kcal mol-1. This method is then applied to construct the potential energy surface for all the reaction systems. High-pressure limit rate constants at 500-2500 K are calculated through variation transition state theory and conventional transition state theory, including a one-dimensional hindered rotor treatment and asymmetrical Eckart tunneling correction. The branching ratio analysis suggests that the hydrogen abstraction at the C site adjacent to the NH2 functional group (α reaction site) dominates the reactions. Linear Bell-Evans-Polanyi and Bell-Evans correlations are observed for the hydrogen abstractions at the C reaction sites. Furthermore, a scheme to estimate the rate constants for the CnH2n+1-NH2 + HO2 reaction system is presented.

Effects of Anharmonicity, Recrossing, Tunneling, and Pressure on the H-Abstractions from Dimethylamine by Triplets O and O2.

Rate constants of the H-abstraction reactions from dimethylamine (DMA) by triplets O and O2 are theoretically determined with the canonical variational transition-state theory (CVT). By comparing the barrier heights and reaction energies obtained from different density-functional theory methods to those computed from the gold-standard method CCSD(T)/CBS(T-Q), we identify the M08-HX/ma-TZVP method as the best with a mean unsigned deviation of 1.0 kcal mol-1. On the basis of the optimized geometries and frequencies with the selected method, the rate constants are calculated using the CVT method combined with the multistructural torsional anharmonicity and small-curvature tunnelling (MS-CVT/SCT) options in the temperature range 200-2000 K. The calculations show that OH and HO2 are mainly produced from the direct abstraction from the C-H bond. The multistructural torsional anharmonicity has a large contribution to the rate constants, and the effects of recrossing and tunneling at the N-site are more important than those at C-site. Additionally, given the formation of reactant complex between DMA and triplet O, the H-abstraction channel is not favored at high pressure. Our calculations with both the Polyrate and MESS codes agree with the reported data within the uncertainty.

Low-threshold upconverted single-mode lasing from CdS hexagonal microcavities.

Upconversion micro/nanolasers are promising in fundamental physics research and practical applications. However, due to the limitation of gain medium and cavity quality, such lasers still suffer from a high lasing threshold (P th). Herein, upconverted whispering-gallery-mode lasing by two-photon absorption is achieved from CdS microplatelets with single-mode emission and low threshold (∼1.2 mJ cm-2). The threshold is three times lower than the best reported value in previous CdS upconversion lasers. Moreover, wavelength-tunable upconverted single-mode lasing is demonstrated from 510.4 to 518.9 nm with narrow linewidths around 0.85 nm, which is further verified through numerical simulations. In addition, the size-dependent lasing behavior is realized from single-mode to multimode oscillation; the corresponding lasing threshold decreases with increasing cavity edge length (L), following a P th ∝ 1/L 2 relationship. These results underscore the promise of CdS microplatelets for developing chip-level frequency upconversion lasers.

Kinetic modeling of methyl pentanoate pyrolysis based on ab initio calculations.

Recently, methyl pentanoate (MP) was proposed as a viable biodiesel surrogate to petroleum-based fuels. To better understand the pyrolysis chemistry of MP, the unimolecular decomposition kinetics of MP is theoretically investigated on the basis of ab initio calculations; ten primary channels, including four intramolecular H-shifts and six C-C and C-O bond fissions, are identified. The geometries are optimized at the M06-2X/cc-pVTZ level of theory, and accurate barrier heights are determined using the DLPNO-CCSD(T)/CBS(T-Q) method, which shows a good performance against the CCSD(T)/CBS(T-Q) method with an uncertainty of 0.5 kcal mol-1 for small methyl esters. The atomization enthalpy method is adopted to obtain the thermodynamics of involved species. The Rice-Ramsperger-Kassel-Marcus/master equation theory coupled with one-dimensional hindered rotor approximation is employed to calculate the phenomenological rate constants at 500-2000 K and 0.01-100 atm. The branching ratio analysis indicates that two reactions, MP ↔ CH3OC([double bond, length as m-dash]O)CH3 + CH2CHCH3 and MP ↔ CH3OC([double bond, length as m-dash]O)CH2 + CH2CH2CH3, are the dominant channels at low and high temperatures, respectively. The model from Diévart et al. [Proc. Combust. Inst., 2013, 34(1), 821-829] is updated with our calculations, and the modified model can yield a better prediction in reproducing the ignition delay times of MP at high temperatures. This work provides a comprehensive investigation of MP unimolecular decomposition, and can serve as a prototype for understanding the pyrolysis of larger alkyl esters.

Benchmarking dual-level MS-Tor and DLPNO-CCSD(T) methods for H-abstraction from methyl pentanoate by an OH radical.

Methyl pentanoate (MP) was recently proposed as a potential biodiesel surrogate due to its negative temperature coefficient region. To provide a basis for constructing an accurate mechanism, chemical kinetics of H-abstraction from MP by an OH radical are investigated theoretically at 200-2000 K. M06-2X/cc-pVTZ is applied for geometry optimizations and frequency calculations. Given the long alkyl-chain in MP, the multi-structural torsional anharmonicity is characterized by using the dual-level MS-T method due to its relatively low computational cost and established accuracy. In particular, AM1 and M06-2X/cc-pVTZ are adopted as low-level and high-level methods in dual-level MS-T, respectively. The results of dual-level MS-T are further used to benchmark against the full high-level method (M06-2X/cc-pVTZ), leading to an uncertainty of less than 30% in the high temperature range. For the single-point energy calculations, the lower computational cost DLPNO-CCSD(T) method is first used to benchmark against the gold-standard method CCSD(T) for small methyl ester (C2-C4) + OH reaction systems, yielding an overestimation of less than 1.1 kcal mol-1 for barrier height; it is then used to refine the electronic energies for the present reaction system MP + OH. Phase-space theory and conventional transition state theory are used to calculate the H-abstraction rate constants. After compensating the uncertainty of barrier height, the calculated phenomenological H-abstraction rate constants agree well with the experimental data at 263-372 K. Branching ratio analysis indicates that the ß-site H abstraction is the dominant channel at 200-1200 K due to its lowest barrier height.

Chemical kinetics of H-abstractions from dimethyl amine by H, CH3, OH, and HO2 radicals with multi-structural torsional anharmonicity.

Dimethyl amine (DMA) is identified as a promising nitrogen-containing fuel candidate. To better understand the atmospheric and combustion chemistry of aliphatic amines, we systematically investigate the reaction kinetics of H-abstractions from DMA by H, CH3, OH, and HO2 radicals in a broad temperature range (100-2000 K). The BHandHLYP/cc-pVTZ method is adopted to determine the optimized geometries and frequencies, and the multi-structural torsional anharmonicity method (MS-T) is employed to characterize the effects of multi-conformer and torsional coupling for the involved species. High-level methods CCSD(T) and CCSD(T)-F12 combined with cc-pVXZ (X = D, T, Q), cc-pVXZ-F12 (X = D, T), and jun-cc-pV(T+d)Z basis sets are used to refine the electronic energies. The results of the gold standard method CCSD(T)/CBS(D-T-Q) with the zero point energy correction are adopted for the kinetic calculations. For the DMA + H/CH3 reactions, the conventional transition state theory (cTST) as well as one-dimensional Eckart tunneling correction is adopted. But for the DMA + OH/HO2 reactions, the reactant-complex (RC) is formed with a deep well (-6.4 and -11.7 kcal mol-1 for RC3 and RC4, respectively), due to the strong hydrogen bonding between the reactants. Hence, the variational transition state theory (VTST) combined with cTST is used to calculate the rate constants. The Rice-Ramsperger-Kassel-Marcus/master equation method is employed to determine the pressure-dependent rate constants in the pressure range of 0.001-100 atm. Our calculations are in agreement with previous experimental measurements and show well the trend in a broad temperature range. In addition, a pronounced pressure-dependence is observed under 400 K, indicating that pressure impacts the reaction mechanisms especially at atmospheric or interstellar temperatures.

Deformation of high density polyethylene by dynamic equal-channel-angular pressing.

The effect of high strain rate and large shear deformation on the orientation of crystallites in high density polyethylene (HDPE) was investigated with dynamic equal-channel-angular pressing (D-ECAP). The HDPE samples were processed by two loading routes, route A and route C. Grid lines were used to obtain macroscopic strain distributions, which were substantiated by finite element modeling. Owing to the strain rate effect, the number of D-ECAP processing passes has a minor effect on the shear strain accumulations compared to ECAP. D-ECAP leads to a decrease in the thickness of the crystalline stem, and the crystallinity. After route-A or route-C D-ECAP processing, a new monoclinic phase emerges, and two types of crystallographic c-axis orientations appear: the crystallographic c-axis is approximately parallel to the flow direction (FD), or is tilted at approximately 55° clockwise away from FD. However, only one type of crystallographic c-axis orientation is detected after 2 passes of route-C D-ECAP. It is viable to utilize D-ECAP to control the structure and orientation of crystalline polymers, as a complement to ECAP and other processing techniques.

Polymer-based micro/nanowire structures for three-dimensional photonic integrations.

By assembling polymer micro/nanowires, 3D wire structures for photonic integrations were fabricated, including a 2x2 crossed structure, a 3x3 crossed structure, and a parallelogram structure. Optical wave-guiding properties of the 3D wire structures were demonstrated with a measured insertion loss of 0.83 dB, on average, at 650 nm wavelength. Light can be transmitted vertically from one wire to another. Coupling efficiency between adjacent wires is tunable by changing the cross angle and the center-to-center distance.