Calculation of proton coupling constants for dibenzothiophene radical anion

The calculation of proton hyperfine coupling constants for dibenzothiophene radical anion is reported.     

Potential energy surface of thionylimide

The potential energy surface (PES) of thionylimide has been searched using ab initio MO and density functional calculations. The electronic structures of the isomers of HNSO have been studied using the HF/6‐31+G*, MP2(full)/6‐31+G*, and B3LYP/6‐31+G* levels. Final energies of these molecules have been calculated at the high‐accuracy G2 and CBS‐Q levels. The probable pathways of isomerization of thionylimide to its isomers (e.g., thiocyanic acid, HONS, nitrosothiols) have been explored by studying the three‐ or four‐membered transition states. This study identified total eight possible isomers ( 1–8 ) of HNSO, of which four ( 1–4 ) have already been realized experimentally. Of the remaining four ( 5–8 ), at least two ( 5, 7 ) can be generated experimentally. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Redox reactivity and reorganization energy of zinc cytochrome c cation radical

Little is known about transient intermediates in photoinduced electron-transfer reactions of metalloproteins. Oxidative quenching of the triplet state of zinc cytochrome c, 3Zncyt, is done at 20 degrees C, pH 7.00, and ionic strength of 1.00 M, conditions that suppress the thermal back-reaction and prolong the lifetime of the cation radical, Zncyt+. This species is reduced by [Fe(CN)6]4-, [W(CN)8]4-, [Os(CN)6]4-, [Mo(CN)8]4-, and [Ru(CN)6]4- complexes of similar structures and the same charge. The rate constants and thermodynamic driving forces for these five similar electron-transfer reactions were fitted to Marcus theory. The reorganization energy of Zncyt+ is lambda = 0.38(5) eV, lower than that of native cytochrome c, because the redox orbital of the porphyrin cation radical is delocalized and possibly because Met80 is not an axial ligand to the zinc(II) ion in the reconstituted cytochrome c. The rate constant for electron self-exchange between Zncyt+ and Zncyt, k11 = 1.0(5) x 10(7) M(-1) s(-1), is large owing to the extended electron delocalization and relatively low reorganization energy. These results may be relevant to zinc(II) derivatives of other heme proteins, which are often used in studies of photoinduced electron-transfer reactions.     

Potential energy surface crossings and the mechanistic spectrum for intramolecular electron transfer in organic radical cations.

The structure of the potential energy surface for the intramolecular electron transfer (IET) of four different model radical cations has been determined by using reaction path mapping and conical intersection optimization at the ab initio CASSCF level of theory. We show that, remarkably, the calculated paths reside in regions of the ground-state energy surface whose structure can be understood in terms of the position and properties of a surface crossing between the ground and the first excited state of the reactant. Thus, in the norbornadiene radical cation and in an analogue compound formed by two cyclopentene units linked by a norbornyl bridge, IET proceeds along direct-overlap and super-exchange concerted paths, respectively, that are located far from a sloped conical intersection point and in a region where the excited-state and ground-state surfaces are well separated. A second potential energy surface structure has been documented for 1,2-diamino ethane radical cation and features two parallel concerted (direct) and stepwise (chemical) paths. In this case a peaked conical intersection is located between the two paths. Finally, a third type of energy surface is documented for the bismethyleneadamantane radical cation and occurs when there is, effectively, a seam of intersection points (not a conical intersection) which separates the reactant and product regions. Since the reaction path cannot avoid the intersection, IET can only occur nonadiabatically. These IET paths indicate that quite different IET mechanisms may operate in radical cations, revealing an unexpectedly enriched and flexible mechanistic spectrum. We show that the origin of each path can be analyzed and understood in terms of the one-dimensional Marcus-Hush model.     

Potential energy surface of 1,6-Methano

The potential energy surface of 1,6-methano[10]annulen-11-ylidene and its isomers has been investigated by density functional (BLYP and B3LYP) molecular orbital methods. These calculations indicate the lowest energy annulene structure to be 56.9 kcal mol(-)(1) higher in energy than triplet 1-naphthylcarbene. These calculations, together with calculations on transition states connecting possible rearrangement products derived from this carbene, indicate that the trapping products reported by Carlton et al. J. Am. Chem. Soc. 1976, 98, 6068-6070 arise from rearrangement of the annulene-carbene to a tricyclic isomer.     

Molecular orbital study of proton hyperfine splitting constants in H 2CN radical

A hyperconjugated model is used to calculate the proton h. f. s. constants in H ₂CN radical by the m. o. method. Agreement with experiment is excellent. A comparison between various approximations employed gives strong evidence of the importance of configuration interaction in such calculations.

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Zusammenfassung Mittels eines hyperkonjugierten Modells werden die Protonenhyperfeinstrukturkonstanten im H ₂CN-Radikal nach der MO-Methode berechnet. Die Übereinstimmung mit dem Experiment ist ausgezeichnet. Der Vergleich verschiedener Näherungsmethoden beweist die Notwendigkeit, bei derartigen Rechnungen Konfigurationswechselwirkung einzuschließen.

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Résumé A l'aide d'un modèle à hyperconjugaison, les constantes de structure hyperfine protonique du radical H ₂CN ont été calculées par la méthode MO. L'accord avec l'expérience est excellent. Une comparaison entre les différentes approximations employées met en évidence l'importance de l'interaction de configuration dans de tels calculs.

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We thank the Italian National Research Council (Chemistry Committee, Research Group IV) for financial support. One of us (P.L.N.) is grateful to Sicedison S.p.A. for a grant.     

OCS电子基态势能面与振动光谱的理论研究

本文采用键长-键角内标系下的自洽场-组态相互作用方法精确计算了OCS分子的振动高激发态能级,并结合实验观测到的振动能级利用非线性最小二乘法优化电子基态势能函数中的势能参数。由优化所得的势能面计算出的振动激发态能级与50个实验观测到的振动能级比较,标准偏差为0.08cm^-^1。此外,还用该势能面计算了OCS同位素分子的振动能级,计算结果与实验值也十分吻合。     

Potential energy surface for the hydrogen molecule-helium system

The results of an ab initio calculation of the potential energy surface governing atomic hydrogen recombination in the presence of helium atoms are presented.     

Transannular distance dependence of stabilization energy of the intramolecular dimer radical cation of cyclophanes

The intramolecular dimer radical cation and charge-transfer complex of various cyclophanes were investigated by using pulse radiolysis measurements. The charge resonance band due to the dimer radical cation of cyclophanes appeared in the near-IR region, which showed a blue-shift as the distance between the two benzene rings of cyclophane decreased. The stabilization energy of the dimer radical cation, which was estimated from the peak position of the charge resonance band, was explained by the exchange interaction, while the substituent effect was small. The absorption peak of the charge-transfer complex with chlorine atom also showed the shift in accordance with the oxidation potential of cyclophanes.     

A nonelectrocyclic path from the cyclobutene cation radical to the 1,3-butadiene cation radical

The conversion of the cyclobutene cation radical to the 1,3-butadiene cation radical has been studied using MINDO /3 and ab initio SCF MO methods. Not only smooth electrocyclic but also stepwise, non-electrocyclic routes were considered. Both calculational methods agree that the preferred reaction path is a novel nonelectrocyclic one proceeding through an intermediate “cyclopropylcarbinyl cation radical.” The quantitative agreement in the activation parameters calculated by the two methods is excellent. The proposed intermediate also provides an attractive explanation for the mass spectrometric fragmentation patterns of the cyclobutene and butadiene cation radicals.     

Dissociation of toluene cation: a new potential energy surface

The potential energy surface (PES) for the formation of tropylium and benzylium ions from toluene cation (1) has been explored theoretically. Quantum chemical calculations at the B3LYP/6-311++G and G3//B3LYP levels were performed. A pathway to form o-isotoluene (5-methylene-1,3-cyclohexadiene) cation (5) from 1 was found. The isomerization occurs by two consecutive 1,2-H shifts from CH(3) to the ortho position of the aromatic ring via a distonic benzenium cation (2), which is also an intermediate in the well-known isomerization of 1 to cycloheptatriene cation (4). Since the barrier for the formation of 2 is the highest in the two isomerization pathways, 1, 4, and 5 are interconvertible energetically prior to dissociation. The benzylium ion can be produced via 5 as well as from 1 and the tropylium ion via 4. Rice-Ramsperger-Kassel-Marcus model calculations were carried out based on the obtained PES. The result agrees with previous experimental observations. From a theoretical analysis of kinetics of the isomerizations and dissociations, we suggest that 5 plays an important role in the formation of C(7)H(7)(+) from 1.     

Experimental and theoretical study on cation radicals of cyclopropane,cyclobutane and cyclopentane

Cation radicals of cycloalkanes have been produced for the first time in γ-irradiated rigid solutions using fluoromethane as a matrix. Observed ESR spectra are analyzed by ab initio MO calculations; molecular geometries of the cations are optimized for several low-lying doublet states by the energy gradient method. Based on the optimized geometry thus determined the hyperfine splitting constants are calculated by the pseudo-orbital theory. Large Jahn-Teller distortions are calculated for the carbon rings and the H-C-H frames of the cation radicals. The distortions are consistent with the nodal picture of singly occupied orbitals. The calculated hfs constants are sensitive to the change in geometry due to a large contribution of spin-delocalization. The average of the calculated proton hfs constants is compatible with the observed ESR spectra which indicates that all the protons of the individual cations have become equivalent owing to the dynamic Jahn-Teller distortion.     

HSCCS自由基势能面的理论研究

在CCSD(T)/6-311G(d,f)//MP2/6-311G(d,f) ZPE水平下,计算得到含有8个异构体和11个过渡态的HSCCS自由基体系势能面,讨论了异构体的结构与稳定性及异构体之间的异构化过程.结果表明异构体m1的能量最低,除m1以外,异构体m2和m3的能量也比较低,在MP2水平上,过渡态TS1的能量比异构体m2仅高3.9kJ/mol,而在CCSD(T)水平上,TS1的能量比m2低14.6 kJ/mol,这说明异构体m2可以迅速转化为能量更低的m1.异构体m3的能量比异构体m1高49.99 kJ/mol,可以推断,在合适的实验条件下可以观测到异构体m1.     

Potential energy surface and rovibrational states of the ground Ar-HI complex

A potential energy surface for the ground electronic state of the Ar-HI van der Waals complex is calculated at the coupled-cluster with single and double excitations and a noniterative perturbation treatment of triple excitations [CCSD(T)] level of theory. Calculations are performed using for the iodine atom a correlation consistent triple-zeta valence basis set in conjunction with large-core Stuttgart-Dresden-Bonn relativistic pseudopotential, whereas specific augmented correlation consistent basis sets are employed for the H and Ar atoms supplemented with an additional set of bond functions. In agreement with previous studies, the equilibrium structure is found to be linear Ar-I-H, with a well depth of 205.38 cm(-1). Another two secondary minima are also predicted at a linear and bent Ar-H-I configurations with well depths of 153.57 and 151.57 cm(-1), respectively. The parametrized CCSD(T) potential is used to calculate rovibrational bound states of Ar-HI/Ar-DI complexes, and the vibrationally averaged structures of the different isomers are determined. Spectroscopic constants are also computed from the CCSD(T) surface and their comparison with available experimental data demonstrates the quality of the present surface in the corresponding configuration regions.     

Potential energy curves and calculations of spectroscopic constants for the ground state of AlC and AlN

The density functional theory method with B3LYP/6-311++G(df,pd), B3LYP/6-311++G(2df, 2pd), and B3LYP/6-311++G(3df,3pd) basis sets is used to compute the geometrics and single point energy of aluminum carbide (AlC) and aluminium nitride (AlN) in their ground state. The Level 8.0 program is used to calculate spectroscopic constants and fit the energy potential curves. The effect of a basis set on the spectroscopic constants is discussed. The results show that the calculated potential curve matches well with the Level 8.0 fitting curve, and the calculated values of spectroscopic constants become more reliable with the improvement of the quality of basis sets. The spectroscopic constants are in good agreement with the existing experimental and theoretical values. For the first time, the reliable anharmonicity constant data of AlC are reported, which agrees so well with the experimental value.