EPR Equilibration Study of the O–H Bond Dissociation Enthalpy in a Benzyl Phenolic Antioxidant

The equilibrium of the reaction galvinoxyl radical + 4,4′-methylene-bis(2,6-di-tert-butyl-phenol) (IOH) ⇆ hydrogalvinoxyl + 4,4′-methylene-bis(2,6-di-tert-butyl-phenoxyl radical) was monitored by electron paramagnetic resonance spectroscopy between 213 and 293 K. The equilibrium constant was calculated for each temperature point and correlated to T ⁻¹ applying the Van't Hoff relationship lnK _R = (−ΔH _R ⁰/RT) + (ΔS _R ⁰/R). The reaction enthalpy was found to be 12.0 ± 0.9 kJ/mol and the bond strength in IOH (BDE_(O–H)) = 340.7 ± 3.0 kJ/mol. The thermochemical stabilization of the involved phenoxyls is discussed. Authors' address: Sara N. Mendiara, Departamento de Química, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Mar del Plata, Funes 3350, Mar del Plata 7600, Argentina     

Infrared diode laser spectroscopy of the Kr–N2O van der Waals complex: the v 1 symmetric stretch region of N2O

The rovibrational spectra of four isotopomers of the Kr–N₂O van der Waals complex, namely ⁸²Kr–N₂O, ⁸³Kr–N₂O, ⁸⁴Kr–N₂O and ⁸⁶Kr–N₂O, were measured in the v ₁ vibrational band region of the N₂O monomer (～1285?cm^?1) using a tunable diode laser spectrometer to probe a pulsed supersonic slit jet. Rotational constants for both ground and excited vibrational states of these four isotopomers were accurately determined. The band-origin of Kr–N₂O was observed to shift by +0.1065?cm^?1 from that of the monomer. The band-origin shifts of Rg–N₂O (Rg?=?Ne, Ar, Kr) in the v ₁ vibrational band region could also be well explained by the model based on a Buckingham intermolecular potential [W.A. Herrebout, H.-B. Qian, H. Yamaguchi and B.J. Howard, J. Mol. Spectrosc. 189, 235 (1998)]. But the band-origin shift of He–N₂O was found to deviate significantly from this model. The possible reason is discussed and the band-origin shift of Xe–N₂O predicted.     

Isotopic effects of the N(2D) + H2 → NH + H reaction: a quantum time-dependent wave packet investigation

Based on the potential energy surface reported by Li and co-workers (J. Comput. Chem. 34 1686–1696 (2013)), the dynamics calculations of N(²D)?+?H₂(v ₀?=?0, j ₀?=?0) reaction and its isotopic variants HD and D₂ are studied using time-dependent wave packet method in the collision energy range of 0.01–1.0?eV. Dynamics properties such as reaction probability, differential cross section, and integral cross section are studied at state-to-state level of theory. Present values are compared with available theoretical and experimental results. The results indicate that the integral cross sections of N(²D)?+?D₂ reaction are in general good agreement with the experimental data at collision energy below 0.15?eV. The rotational state-resolved integral cross sections of N(²D)?+?H₂/HD/D₂ reactions are compared with experimental values for the first time, with the obtained values being in good agreement with the experimental data.     

Hydrogen CARS thermometry in a high-pressure H2–air flame. Test of H2 temperature accuracy and influence of line width by comparison with N2 CARS as reference

This work describes a further step towards the determination of the temperature accuracy of H₂ Q-branch CARS (Coherent Anti-Stokes Raman Scattering) at high pressure with regard to the influence of the H₂ line widths. In laminar steady H₂/air flames in the pressure range 1–15 bar and at fuel-rich conditions with stoichiometries between two and four, quasi-simultaneous temperature measurements were performed with H₂ and N₂ CARS. The temperature values deduced from H₂ CARS are in good agreement with the reference temperature from N₂ CARS. The influence of different line-width contributions on the accuracy of H₂ Q-branch thermometry was investigated in detail. Received: 10 April 2001 / Revised version: 22 May 2001 / Published online: 18 July 2001     

13C NMR Measurement of Hydrogen Bonding Effects for Benzylic Alcohol- Φ Or N Base Complexes : Relationship Between the Oh Stretching Frequencies and the Chemical Shifts of Proton Donor Groups

The carbon shifts induced by hydrogen bonding have been measured for complexes between benzylic alcohol and Φ or n bases (from benzene to collidine) of largely varied strengths. Linear relationships are obtained between corrected induced shifts and the IR frequency shifts Δν_OH but reverse slopes result for the C-1 and C-α carbons of benzylic alcohol.     

Study of n-γ discrimination for 0.4-1 MeV neutrons using the zero-crossing method with a BC501A liquid scintillation detector

An experimental system aimed at n-γ discrimination using the zero-crossing method with a φ3’’×2’’ BC501A liquid scintillation detector was established and tested with an Am-Be neutron source. Two-dimensional plots of energy versus zero-crossing time were obtained. The quality of n-γ discrimination was checked by the figure-of-merit (FOM), the neutron peak-to-valley ratio, and the proportion of leaked neutrons over all neutron events. The performance of n-γ discrimination in terms of FOM was compared with previous work done by other groups. The n-γ discrimination in four different energy regions with an interval of 0.1 MeV between 0.3 MeV and 0.7 MeV was studied, and the results indicate that the n-γ discrimination threshold can go down to 0.4 MeV.     

Properties of cationic pnicogen-bonded complexes F4-nHnP+:N-base with H–P···N linear and n = 1–4

Ab initio MP2/aug'-cc-pVTZ calculations have been carried out to investigate the pnicogen-bonded complexes F_4-nH_nP⁺:N-base, for n = 1–4, each with a linear or nearly linear H_ax–P···N alignment. The sp³-hybridised nitrogen bases include NH₃, NClH₂, NFH₂, NCl₂H, NCl₃, NFCl₂, NF₂H, NF₂Cl, and NF_3, and the sp bases are NCNH₂, NCCH₃, NP, NCOH, NCCl, NCH, NCF, NCCN, and N₂. Binding energies increase as the P–N distance decreases, with an exponential curve showing this relationship when complexes with sp³ and sp hybridised bases are treated separately. However, the correlations are not as good as they are for the complexes F_4-nH_nP⁺:N-base for n = 0–3 with F–P···N linear. Different patterns are observed for the change in the binding energies of complexes with a particular base as the number of F atoms in the acid changes. Thus, the particular acid–base pair is a factor in determining the binding energies of these complexes.

Three different charge-transfer interactions stabilise these complexes, namely N_lp→σ*P–H_ax, N_lp→σ*P–F_eq, and N_lp→σ*P–H_eq. Unlike the corresponding complexes with F–P···N linear, N_lp→σ*P–H_ax is not always the dominant charge-transfer interaction, since N_lp→σ*P–F_eq is greater in some complexes. N_lp→σ*P–H_eq makes the smallest contribution to the total charge-transfer energy. The total charge-transfer energies of all complexes increase exponentially as the P–N distance decreases in a manner very similar to that observed for the series of complexes with F–P···N linear.

Equation-of-motion coupled cluster singles and doubles (EOM-CCSD) spin–spin coupling constants ^1pJ(P–N) across the pnicogen bond vary with the P–N distance, but different patterns are observed which depend on the nature of the acid, and for some acids, on the hybridisation of the nitrogen base. ^1pJ(P–N) values for complexes of F₃HP⁺ initially increase as the P–N distance decreases, reach a maximum, and then decrease with decreasing P–N distance as the P···N bond acquires increased covalent character. ^1pJ(P–N) for complexes with H–P···N linear and those with F–P···N linear exhibit similar distance dependencies depending on the number of F atoms in equatorial positions and the hybridisation of the base. Complexation may increase, decrease, or leave the P–H_ax distance unchanged, but ¹J(P–H_ax) always decreases relative to the corresponding isolated ion. Decreasing ¹J(P–H_ax) can be related to decreasing intermolecular P–N distance.     

Study of n-γ discrimination for 0.4-1 MeV neutrons using the zero-crossing method with a BC501A liquid scintillation detector

An experimental system aimed at n-γ discrimination using the zero-crossing method with a φ3"× 2" BC501A liquid scintillation detector was established and tested with an Am-Be neutron source. Two-dimensional plots of energy versus zero-crossing time were obtained. The quality of n-γ discrimination was checked by the figure-of-merit (FOM), the neutron peak-to-valley ratio, and the proportion of leaked neutrons over all neutron events. The performance of n-γ discrimination in terms of FOM was compared with previous work done by other groups. The n-γ discrimination in four different energy regions with an interval of 0.1 MeV between 0.3 MeV and 0.7 MeV was studied, and the results indicate that the n-γ discrimination threshold can go down to 0.4 MeV.     

Rotational components of the v8 = 1, 2, and 3 and ground vibrational levels of CH3C15N for the frequency range 17–75 GHz

The microwave spectrum of methyl cyanide CH₃C¹⁵N was studied for the v₈ = 3 vibrational state in the frequency range of 17 to 75 GHz. In addition, some rotational components for the ground, v₈ = 1 and 2 were remeasured and these results compared to those found in the literature. The frequencies of 42 components were measured and these frequencies were used to produce a constant set which can be used to predict overall frequencies of spectral components in the ground, v₈ = 1, 2 up to an accuracy of 100 KHz and those for v₈ = 3, 4 up to an accuracy of 150 KHz. Previously obtained experimental data, available from the literature, and our own data for the ground, v₈ = 1 and 2, and the new data for v₈ = 3 are presented and compared with the frequencies obtained from a comprehensive equation derived from perturbation techniques.     

Study of Events with an Electron,Muon, and Two Hadron Jets in the Final State with an Integrated Luminosity of a 139 fb–1 in pp Collisions at $$\sqrt s $$ = 13 TeV with the ATLAS Detector at the LHC

Physics of Atomic Nuclei - To investigate the Higgs boson properties in the h → WW* → еνμν decay channel, events with an electron, muon, and two hadron jets in the...     

Quantitative Measurement of Transverse and Longitudinal Cross-Correlation between13C–1H Dipolar Interaction and13C Chemical Shift Anisotropy: Application to a13C-Labeled DNA Duplex

Measurement of both longitudinal and transverse relaxation interference (cross-correlation) between¹³C chemical shift anisotropy and¹³C–¹H dipolar interactions is described. The ratio of the transverse to longitudinal cross-correlation rates readily yields the ratio of spectral densitiesJ(0)/J(ω_C), independent of any structural attributes such as internuclear distance or chemical shift tensor. The spectral density at zero frequencyJ(0) is also independent of chemical exchange effects. With limited internal motions, the ratio also enables an accurate evaluation of the correlation time for overall molecular tumbling. Applicability of this approach to investigating dynamics has been demonstrated by measurements made at three temperatures using a DNA decamer duplex with purines randomly enriched to 15% in¹³C.     

Crystal growth and characterization of a novel inorganic–organic hybrid NLO crystal: (NH4)[Cd(NCS)3]·C12H24O6

It is reported here, for the first time, that high-quality bulk size (18 × 5 × 4 mm³) single crystals of a new nonlinear optical crystal, [(NH₄)[Cd(NCS)₃]·C₁₂H₂₄O₆] [Ammonium (18-crown-6-ether) Cadmium(II) tri-thiocyanate; ACCTC], have been grown from aqueous solution via slow evaporation technique. Solubility of ACCTC has been determined for various temperatures. The grown crystals were characterized by single crystal X-ray diffraction, FT-IR, FT-Raman, and UV–Vis–NIR studies. ACCTC crystallizes in orthorhombic system with cell parameters a = 14.7568 ?, b = 15.4378 ?, and c = 10.6383 ? with space group Cmc2₁. The optical second-harmonic generation effect has been measured by using the Kurtz powder technique and is found to be 2 times higher than that of KDP (KH₂PO₄). The sample possesses wide optical transparency range from 200 to 2,500 nm. The TG-DSC thermal analysis revealed that the sample is thermally stable up to 237.92 °C, which is comparatively far better than the thermal stability of [(18C6)Li][Cd(SCN)₃]; CLTC (170 °C).     

Hydrogen spin flip satellite lines associated with the PO2−3 radical in a single crystal of Na2HPO3· 5H2O : Calculated and experimental intensities

Intensities of satellite lines have been calculated for PO²⁻₃ in a single crystal of Na₂HPO₃·5H₂O, based on the known crystallographic structure and unpaired spin distribution in the radical. It was assumed that water protons contribute to the satellite intensity. Variation of the satellite intensity was calculated in the bc plane and data were compared with measured intensities at two orientations. At X-band (9 GHz) the experimental intensity is greater than the calculated intensity by a factor of 3 to 4, probably because of overlap with and borrowed intensity from the main line and the inadequacy of the high field approximation. At Q-band (35 GHz) there is good agreement between the calculated and experimental intensities within 10–20 %. It seems that measurements at higher microwave frequency are more reliable than those at lower microwave frequency for the derivation of the electron-proton distances.     

Generation of Intense Near and Mid-Infrared Femtosecond Radiation (1.2–2.4 μm) with the Use of the Broadband Parametric Down-Conversion in a Type-II BBO Crystal Pumped by a Ti:Sapphire Laser and Its Application for the Generation of Terahertz Radiation in Organic Crystals

JETP Letters - A two-stage optical parametric amplifier is fabricated on the basis of type-II BBO crystals pumped by the intense radiation of a Ti:sapphire laser. Femtosecond radiation tunable from...     

The infrared spectrum of 13C2H2 in the 60–2600 cm−1 region: bending states up to v 4 + v 5 = 4

The vibration–rotation spectra of ¹³C substituted acetylene, ¹³C₂H₂, have been recorded in the region between 60 and 2600?cm^?1 at an effective resolution ranging from 0.001 to 0.006?cm^?1. Three different instruments were used to collect the experimental data in the extended spectral interval investigated. In total 9529 rotation vibration transitions have been assigned to 101 bands involving the bending states up to v _tot?=?v ₄?+?v ₅?=?4, allowing the characterization of the ground state and of 33 vibrationally excited states. All the bands involving states up to v _tot?=?3 have been analyzed simultaneously by adopting a model Hamiltonian which takes into account the vibration and rotation l-type resonances. The derived spectroscopic parameters reproduce the transition wavenumbers with a RMS value of the order of the experimental uncertainty. Using the same model, larger discrepancies between observed and calculated values have been obtained for transitions involving states with v _tot?=?4. These could be satisfactorily reproduced only by adopting a set of effective constants for each vibrational manifold, in addition to the previously determined parameters, which were constrained in the analysis.     

The infrared spectrum of 13C2HD between 100 and 2100 cm−1: a global fit for the bending states up to υ 4 + υ 5 = 3

The fundamental bending ro-vibrational bands and a number of overtone, combination and hot bands of ¹³C₂HD have been recorded by Fourier transform infrared spectroscopy in the range 450–2100 cm^?1. In addition, the ν ₅ ← ν ₄ band, centred at 164.65 cm^?1, has been identified in the spectrum of ¹³C₂H₂. The data were analysed simultaneously in a global fit that has provided very accurate rotational and vibrational parameters for the ground and vibrationally excited states.