Computational study of the structure, bonding and reactivity of selected helical metallocenes

Cázares-Larios, U.E.; Reyes-Leaño, U.G.; Castillo-López, P.A.; Pineda‐Urbina, Kayim; Gómez‐Sandoval, Zeferino

doi:10.1016/j.ica.2015.09.017

Cited by 6 publications

(1 citation statement)

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“…The direct solution of the Dirac equation needs large calculations, which can alone deal with small molecules accurately. Zeroth-order regular approximation (ZORA) is a widely used approach for the relativistic calculation with small calculation and high precision, which is adopted to deal with the operator with simple formation [ 54 ]. ZORA Hamiltonian contains scalar-relativistic or spin-orbit coupling [ 55 ].…”

Section: Discussionmentioning

confidence: 99%

Theoretical Studies on Structures, Properties and Dominant Debromination Pathways for Selected Polybrominated Diphenyl Ethers

Shi

et al. 2016

IJMS

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The B3LYP/6-311+G(d)-SDD method, which considers the relativistic effect of bromine, was adopted for the calculations of the selected polybrominated diphenyl ethers (PBDEs) in the present study, in which the B3LYP/6-311+G(d) method was also applied. The calculated values and experimental data for structural parameters of the selected PBDEs were compared to find the suitable theoretical methods for their structural optimization. The results show that the B3LYP/6-311+G(d) method can give the better results (with the root mean square errors (RMSEs) of 0.0268 for the C–Br bond and 0.0161 for the C–O bond) than the B3LYP/6-311+G(d)-SDD method. Then, the B3LYP/6-311+G(d) method was applied to predict the structures for the other selected PBDEs (both neutral and anionic species). The lowest unoccupied molecular orbital (LUMO) and the electron affinity are of a close relationship. The electron affinities (vertical electron affinity and adiabatic electron affinity) were discussed to study their electron capture abilities. To better estimate the conversion of configuration for PBDEs, the configuration transition states for BDE-5, BDE-22 and BDE-47 were calculated at the B3LYP/ 6-311+G(d) level in both gas phase and solution. The possible debromination pathway for BDE-22 were also studied, which have bromine substituents on two phenyl rings and the bromine on meta-position prefers to depart from the phenyl ring. The reaction profile of the electron-induced reductive debromination for BDE-22 were also shown in order to study its degradation mechanism.

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Section: Discussionmentioning

confidence: 99%