A segmented basis set of quadruple zeta valence quality plus polarization functions(QZP)for H through Xe was developed to be used in conjunction with the ZORA Hamiltonian.This set was augmented with diffuse functions ...A segmented basis set of quadruple zeta valence quality plus polarization functions(QZP)for H through Xe was developed to be used in conjunction with the ZORA Hamiltonian.This set was augmented with diffuse functions to describe electrons farther away from the nuclei adequately.Using the ZORA-CCSD(T)/QZP-ZORA theoretical model,atomic ionization energies and bond lengths,harmonic vibrational frequencies,and atomization energies of some molecules were calculated.The addition of core-valence corrections has been shown to improve the agreement between theoretical and experimental results for molecular properties.For atomization energies,a similar observation emerges when considering spin-orbit couplings.With the augmented QZP-ZORA set,static mean dipole polarizabilities of a set of atoms were calculated and compared with previously published recommended and experimental values.Performance evaluations of the ZORA and Douglas–Kroll–Hess Hamiltonians were made for each property studied.展开更多
In order to reveal the reactivity of a functional group in an aromatic compound having two substituents inthe aromatic ring, the hydrogen-isotope exchange reaction (T-H exchange reaction) between tritiated water vapor...In order to reveal the reactivity of a functional group in an aromatic compound having two substituents inthe aromatic ring, the hydrogen-isotope exchange reaction (T-H exchange reaction) between tritiated water vapor(HTO vapor) and 4-amino-2-methylbenzenesulfonic acid (and 5-amino-2-methylphenol) were dynamically observedat 50 (and 70 ) in a gas ℃ ℃ -solid system. Consequently, the fact that the specific activity of the acid increased withtime was obtained, and the T-for-H exchange reaction occurred. By applying the A"-McKay plot method to the dataobserved, the rate constant of each functional group for the reaction was obtained. After the additive property of theHammett’s rule was applied to this work, the new substituent constants were obtained. From the above-mentioned,the following four items have been confirmed: (1) the reactivity of the functional groups can be dynamically analyzed,and the A"-McKay plot method is useful to analyze the reactivity; (2) the additive property of the Hammett’s rule isapplicable to quantitative comparison of the reactivity of the functional groups; (3) the reactivity of the functionalgroups can be simultaneously analyzed by using the A"-McKay plot method in the T-H exchange reaction; and (4) themethod used in this work is also useful for analyzing the reactivity of a certain material having some kinds of functional groups.展开更多
基金the financial support of Conselho Nacional de Desenvolvimento Científico e Tecnológico and Coordenacao de Aperfeic oamento de Pessoal de Nível Superior (Brazilian Agencies)。
文摘A segmented basis set of quadruple zeta valence quality plus polarization functions(QZP)for H through Xe was developed to be used in conjunction with the ZORA Hamiltonian.This set was augmented with diffuse functions to describe electrons farther away from the nuclei adequately.Using the ZORA-CCSD(T)/QZP-ZORA theoretical model,atomic ionization energies and bond lengths,harmonic vibrational frequencies,and atomization energies of some molecules were calculated.The addition of core-valence corrections has been shown to improve the agreement between theoretical and experimental results for molecular properties.For atomization energies,a similar observation emerges when considering spin-orbit couplings.With the augmented QZP-ZORA set,static mean dipole polarizabilities of a set of atoms were calculated and compared with previously published recommended and experimental values.Performance evaluations of the ZORA and Douglas–Kroll–Hess Hamiltonians were made for each property studied.
文摘In order to reveal the reactivity of a functional group in an aromatic compound having two substituents inthe aromatic ring, the hydrogen-isotope exchange reaction (T-H exchange reaction) between tritiated water vapor(HTO vapor) and 4-amino-2-methylbenzenesulfonic acid (and 5-amino-2-methylphenol) were dynamically observedat 50 (and 70 ) in a gas ℃ ℃ -solid system. Consequently, the fact that the specific activity of the acid increased withtime was obtained, and the T-for-H exchange reaction occurred. By applying the A"-McKay plot method to the dataobserved, the rate constant of each functional group for the reaction was obtained. After the additive property of theHammett’s rule was applied to this work, the new substituent constants were obtained. From the above-mentioned,the following four items have been confirmed: (1) the reactivity of the functional groups can be dynamically analyzed,and the A"-McKay plot method is useful to analyze the reactivity; (2) the additive property of the Hammett’s rule isapplicable to quantitative comparison of the reactivity of the functional groups; (3) the reactivity of the functionalgroups can be simultaneously analyzed by using the A"-McKay plot method in the T-H exchange reaction; and (4) themethod used in this work is also useful for analyzing the reactivity of a certain material having some kinds of functional groups.
