Isomer-specific ultraviolet spectroscopy of m- and p-divinylbenzene

The ultraviolet spectroscopy of m- and p-divinylbenzene isomers (mDVB and pDVB) was studied by a combination of methods, including resonance-enhanced two-photon ionization (R2PI), laser-induced fluorescence (LIF), UV-UV hole-burning spectroscopy (UVHB), and single vibronic level fluorescence spectroscopy (SVLF). In mDVB, there are three low-energy conformations, cis-cis, cis-trans, and trans-trans whose S1 <-- S0 origins occur at 31,408, 31,856, and 32,164 cm(-1), respectively, as confirmed by UVHB spectroscopy. There are two possible conformations in pDVB, cis and trans. UVHB studies confirm the S1 <-- S0 origin of trans-pDVB occurs at 32,553 cm(-1), and the corresponding cis-pDVB origin is tentatively assigned to a transition at 32 621 cm(-1). SVLF studies were used to determine several of the vinyl torsional levels of the isomers of mDVB and pDVB. A two-dimensional flexible model was used to fit these levels in mDVB to a potential form and determine the barriers to isomerization.     

Pi and sigma-phenylethynyl radicals and their isomers o-, m-, and p-ethynylphenyl: structures, energetics, and electron affinities

Molecular structures, energetics, vibrational frequencies, and electron affinities are predicted for the phenylethynyl radical and its isomers. Electron affinities are computed using density functional theory, -namely, the BHLYP, BLYP, B3LYP, BP86, BPW91, and B3PW91 functionals-, employing the double-zeta plus polarization DZP++ basis set; this level of theory is known to perform well for the computation of electron affinities. Furthermore, ab initio computations employing perturbation theory, coupled cluster with single and double excitations [CCSD], and the inclusion of perturbative triples [CCSD(T)] are performed to determine the relative energies of the isomers. These higher level computations are performed with the correlation consistent family of basis sets cc-pVXZ (X = D, T, Q, 5). Three electronic states are probed for the phenylethynyl radical. In C2v symmetry, the out-of-plane (2B1) radical is predicted to lie about 10 kcal/mol below the in-plane (2B2) radical by DFT methods, which becomes 9.4 kcal/mol with the consideration of the CCSD(T) method. The energy difference between the lowest pi and sigma electronic states of the phenylethynyl radical is also about 10 kcal/mol according to DFT; however, CCSD(T) with the cc-pVQZ basis set shows this energy separation to be just 1.8 kcal/mol. The theoretical electron affinities of the phenylethynyl radical are predicted to be 3.00 eV (B3LYP/DZP++) and 3.03 eV (CCSD(T)/DZP++//MP2/DZP++). The adiabatic electron affinities (EAad) of the three isomers of phenylethynyl, that is, the ortho-, meta-, and para-ethynylphenyl, are predicted to be 1.45, 1.40, and 1.43 eV, respectively. Hence, the phenylethynyl radical binds an electron far more effectively than the three other radicals studied. Thermochemical predictions, such as the bond dissociation energies of the aromatic and ethynyl C-H bonds and the proton affinities of the phenylethynyl and ethynylphenyl anions, are also reported.     

Vibrational spectroscopic study of o-, m- and p-hydroxybenzylideneaminoantipyrines

Three structurally similar antipyrine derivatives of o-hydroxybenzylideneaminoantipyrine (o-HBAP), m-hydroxybenzylideneaminoantipyrine (m-HBAP) and p-hydroxybenzylideneaminoantipyrine (p-HBAP) were characterized by FT-IR, FT-Raman experimental techniques and density functional theoretical (DFT) calculations. The comparisons between the calculated and experimental results covering molecular structures, assignments of fundamental vibrational modes and thermodynamic properties were investigated. The optimized molecular geometries agree well with the corresponding experimental values by comparing with the XRD data. The comparisons and assignments of the vibrational frequencies indicate that the experimental spectra also coincide satisfactorily with those of theoretically simulated spectrograms except the hydrogen-bond coupling infrared vibrations, and compounds can be distinguished by the IR and Raman spectra due to the differences of the hydroxyl-substituted positions and molecular packing, and the strong Raman scattering activities of the compounds are tightly relative to the molecular conjugative moieties linked through the Schiff base imines. The thermodynamic functions and their correlations with temperatures were also obtained from the theoretical harmonic frequencies.     

Zur Unterscheidung von o-, m- und p-Phenylendiamin

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Magnetic properties and aromaticity of o-, m-, and p-benzyne

The relative aromaticities of the three singlet benzyne isomers, 1,2-, 1,3-, and 1,4-didehydrobenzenes have been evaluated with a series of aromaticity indicators, including magnetic susceptibility anisotropies and exaltations, nucleus-independent chemical shifts (NICS), and aromatic stabilization energies (all evaluated at the DFT level), as well as valence-bond Pauling resonance energies. Most of the criteria point to the o-benzyne相似文献   

The enthalpies of formation of o-, m-, and p-benzoquinone: gas-phase ion energetics, combustion calorimetry, and quantum chemical computations combined

Radical anions of o-, m-, and p-benzoquinone were produced in a Fourier transform mass spectrometer by low energy electron attachment or collision-induced dissociation and were differentiated. Classical derivatization experiments also were carried out to authenticate the ortho and meta anions. Gas-phase techniques were used to measure the proton affinities of all three radical anions and the electron affinities of o- and m-benzoquinone. By combining these results in thermodynamic cycles, we derived heats of hydrogenation of o-, m-, and p-benzoquinone (Delta(hyd)H degrees (1o, 1m, and 1p) = 42.8 +/- 4.1, 74.8 +/- 4.1, and 38.5 +/- 3.0 kcal mol(-)(1), respectively) and their heats of formation (Delta(f)H degrees (1o, 1m, and 1p) = -23.1 +/- 4.1, 6.8 +/- 4.1, and -27.7 +/- 3.0 kcal mol(-)(1), respectively). Good accord with the literature value for the para derivative was obtained. Combustion calorimetry and heats of sublimation also were measured for benzil and 3,5-di-tert-butyl-o-benzoquinone. The former heat of formation agreed with previous determinations, while the latter result (Delta(f)H degrees (g) = -73.09 +/- 0.87 kcal mol(-)(1)) was transformed to Delta(f)H degrees (1o) = -18.9 +/- 2.2 kcal mol(-)(1) by removing the effect of the tert-butyl groups via isodesmic reactions. This led to a final value of Delta(f)H degrees (1o) = -21.0 +/- 3.1 kcal mol(-)(1). Additivity was found to work well for m-benzoquinone, but BDE1 and BDE2 for 1,2- and 1,4-dihydroxybenzene differed by a remarkably small 14.1 +/- 4.2 and 23.5 +/- 3.7 kcal mol(-)(1), respectively, indicating that o- and p-benzoquinone should be excellent radical traps.     

Relativistic multireference calculation of photodissociation of o-, m-, and p-bromofluorobenzene

Quantum chemical calculations with relativistic effects were performed on the photodissociation of o-, m-, and p-bromofluorobenzene (o-, m-, and p-BrFPh) at 266 nm. The method of multistate second-order multiconfigurational perturbation theory in conjunction with spin-orbit interaction through complete active space state interaction was employed to calculate the potential energy curves for the ground and low-lying excited states of o-, m-, and p-BrFPh along their photodissociation reaction coordinates. The dissociation mechanisms with products of Br((2)P(3∕2)) and Br(?)((2)P(1∕2)) states were clarified with the computed potential energy curves and the surface crossings. The current calculations augmented previous theoretical investigations by including relativistic effects and resolved some differences of experimental assignment regarding the dissociation channels of o-, m-, and p-BrFPh.     

Zur gaschromatographischen Analyse von o-, m- und p-Chloronitrobenzol

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Effect of hydrogen bonding on the polymerization of N-(o-,m-, and p-methoxyphenyl)- and N-(o-,m-, and p-ethoxyphenyl)-methacrylamides

Summary Study of the rates of polymerization of N-(o-, m-, and p-methoxyphenyl)- and N-(o-, m-, and p-ethoxy-phenyl)methacrylamides showed that the ortho isomers of these compounds, in which there is no association between the molecules, polymerize much more rapidly than their meta and para isomers, the molecules of which are associated through hydrogen bonds.     

离子色谱法分析邻,间,对硝基苯酚

建立了一种分析邻，间，对硝基苯酚的离子色谱分析体系，选用亚硝酸钠溶液作为淋洗液，紫外检测波长２５４ｎｍ能很好的分析硝基苯酚异构体，检测限低于１０＾－４ｇ／Ｌ。     

镁铝类水滑石对邻、间、对甲基苯酚的吸附

采用液相非稳态共沉淀法制备了镁铝类水滑石（Mg-Al HTlc）,并研究了邻、间和对甲基苯酚在Mg-Al HTlc上的吸附行为。 结果表明,邻、间和对甲基苯酚在Mg-Al HTlc上的吸附等温方程均符合Freundlich吸附等温式;吸附动力学均符合准二级动力学方程;在实验范围内,Mg-Al HTlc对三者的吸附量为：对甲基苯酚＞邻甲基苯酚＞间甲基苯酚;在pH值5.00~13.00范围内,三者的吸附量均随pH值的增加先增大后减小、随温度升高和电解质（NaCl）浓度的增大而增大。 探讨了吸附机理和苯环上甲基取代基位置对吸附的影响。     

薄层色谱法同时测定邻苯二酚、间苯二酚和对苯二酚异构体

研究了在自制硅胶薄板上邻苯二酚,间苯二酚异构体的薄层色谱特性。展开剂为本：乙醚：冰醋酸＝７：２：１（Ｖ／Ｖ／Ｖ）,Ｒｆ值分别为０．５９,０．５３,０．４８。检测限分别为１．０７×１０＾－４,１．６４×１０＾－４,１．９０×１０＾４ｍｏｌ／Ｌ。其他常见酚不干扰测定。可应用于实际样品的测定,回收率为９６％－１０４％。     

The o-, m-, and p-benzyne radical cations: a theoretical study

On the basis of the CASPT2 (multiconfigurational second-order perturbation theory) geometry optimization calculations, the ground states of the o-C(6)H(4)(+) (C(2v)), m-C(6)H(4)(+) (C(2v)), and p-C(6)H(4)(+) (D(2h)) radical cations were determined to be 1 (2)B(1), 1 (2)A(2), and 1 (2)B(1u), respectively. For o-C(6)H(4)(+) and m-C(6)H(4)(+), the first excited states (1 (2)A(2) and 1 (2)A(1), respectively) lie very close to the respective ground states. The small distance value of 1.419 A between the two dehydrocarbons in the ground-state geometry of m-C(6)H(4)(+) indicates that there is a real chemical bond between the two dehydrocarbons (the distance in the 1 (2)A(1) geometry of m-C(6)H(4)(+) is very long as in the m-C(6)H(4) molecule). The (U)B3LYP isotropic proton hfcc (hyperfine coupling constant) calculation results imply that the ground and first excited states of o-C(6)H(4)(+) will have similar ESR spectrum patterns while the ground and first excited states of m-C(6)H(4)(+) will have completely different ESR spectrum patterns.     

Spin-orbit ab initio investigation of the photolysis of o-, m-, and p-bromotoluene

The photodissociations of o-, m-, and p-bromotoluene were investigated by ab initio and spin-orbit ab initio calculations. The possible photodissociation mechanisms at 266 and 193 nm were clarified by multistate second order multiconfigurational perturbation theory (MS-CASPT2) calculated potential energy curves, vertical excitation energies, and oscillator strengths of low-lying states. The dissociation products with spin-orbit-coupled states of Br(*)((2)P(12)) and Br((2)P(32)) were identified by the MS-CASPT2 method in conjunction with spin-orbit interaction through complete active space state interaction (MS-CASPT2/CASSI-SO) calculations. The effects of methyl rotation and substituent on the photodissociation mechanism were discussed.     

Die quantitative Bestimmung von o-, m- und p-Kresolen nach den Infrarotabsorptionsspektren

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