Modeling nonlinear optical properties of inorganic complexes. Counterion effects

Cundari, Thomas R.; Kurtz, Henry A.; Zhou, Tie

doi:10.1016/s0301-0104(98)00365-6

Cited by 7 publications

(12 citation statements)

References 11 publications

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“…53,54 The 6-31+g* basis set and its extensions 6-31+g**, 6-31++g*, 6-31++g**, and 6-311++g** basis sets are respectively used for non-metal atoms. Considering the computational efficiency and accuracy of the ECP, 55,56 the SDD/ECP basis set is used for the transition metal Fe.…”

Section: Computational Detailsmentioning

confidence: 99%

“…We now turn our attention to the basis set extension effect. We calculated the b tot values at the CAM-B3LYP level of theory using the SDD basis set for the Fe ion (as regards the Fe ion, one should always have in mind the difficulties in computing NLO properties of molecules containing transition metal atoms 55 ) and the 6-31+g* basis set and its extensions 6-31+g**, 6-31++g*, 6-31++g**, and 6-311++g** basis sets, respectively, for nonmetal atoms (Table 2). It is worth noting that the 6-31+g* basis set yields values very close to its extensional basis sets.…”

Section: First Hyperpolarizabilitymentioning

confidence: 99%

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Redox control of ferrocene-based complexes with systematically extended π-conjugated connectors: switchable and tailorable second order nonlinear optics

Wang

Sun

et al. 2014

Phys. Chem. Chem. Phys.

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The studies of geometrical structures, thermal stabilities, redox properties, nonlinear responses and optoelectronic properties have been carried out on a series of novel ferrocenyl (Fc) chromophores with the view of assessing their switchable and tailorable second order nonlinear optics (NLO). The use of a constant Fc donor and a 4,4'-bipyridinium acceptor and varied conjugated bridges makes it possible to systematically determine the contribution of organic connectors to chromophore nonlinear optical activities. The structures reveal that both the reduction reactions and organic connectors have a significant influence on 4,4'-bipyridinium. The potential energy surface maps along with plots of reduced density gradient mirror the thermal stabilities of the Fc-based chromophores. The first and second reductions take place preferentially at the 4,4'-bipyridinium moieties. Significantly, the reduction processes result in the molecular switches with large NLO contrast varying from zero or very small to a large value. Moreover, time-dependent density functional theory results indicate that the absorption peaks are mainly attributed to Fc to 4,4'-bipyridinium charge transfer and the mixture of intramolecular charge transfer within the two respective 4,4'-bipyridinium moieties coupled with interlayer charge transfer between the two 4,4'-bipyridinium moieties. This provides us with comprehensive information on the effect of organic connectors on the NLO properties.

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Section: Computational Detailsmentioning

confidence: 99%

Section: First Hyperpolarizabilitymentioning

confidence: 99%

Redox control of ferrocene-based complexes with systematically extended π-conjugated connectors: switchable and tailorable second order nonlinear optics

Wang

Sun

et al. 2014

Phys. Chem. Chem. Phys.

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“…On the basis of the initial results for [MO 4 ] q - ,4a we found that NLO properties of neutral and sometimes less negatively charged inorganic species can be reliably modeled in the gas phase. However, there is a systematic overestimation of polarizabilities (α) and second hyperpolarizabilities (γ) for highly negatively charged species as a consequence of the inherent difficulties in treating such species quantum mechanically in the gas phase.…”

Section: Introductionmentioning

confidence: 96%

“…However, systematic studies of NLO properties of inorganic complexes are comparatively very rare . As an initial effort to fill this void, we have recently studied NLO properties of all the existing transition metal (TM) metalates, [MO 4 ] q - (M: transition metals of groups 4−8 and the first to third transition series, except for Fe; q : charge) . Metalates are simple molecular models for inorganic NLO materials, such as lithium niobate and barium titanate, which belong to the first NLO materials in use.…”

Section: Introductionmentioning

confidence: 99%

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Computational Study of Polarizabilities and Second Hyperpolarizabilities of Inorganic Transition Metal Thiometalates and Metalates in Solution

2000

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A systematic study of nonlinear optical (NLO) properties of inorganic transition metal (TM) thiometalates and metalates is reported. Polarizabilities (R) and second hyperpolarizabilities (γ) are calculated in solution within the polarizable continuum model. It is found that NLO properties of anionic inorganic complexes can be successfully modeled in solution, when this cannot be done so in the gas phase. Solvent effects are found to significantly increase R and γ. The effects are stronger on γ (up to 80%) than on R (up to 40%) and stronger on TM thiometalates than on metalates. For R, solvent effects are found to be more important than electron correlation effects. For γ, the two effects are similarly important. Solvent effects on R and γ caused by subordinate factors other than the dominant electrostatic solute-solvent interactions were studied and assessed to be negligible. Upon solvation, large TM and ligand modification effects on R and γ are found. One oxo-to-sulfido substitution results in an increase in R by 38 au and γ by 10 000 au.

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Relativistic Effects on Magnetic Resonance Parameters and Other Properties of Inorganic Molecules and Metal Complexes

Autschbach

2010

Challenges and Advances in Computational Chemistry and Physics

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Modeling nonlinear optical properties of inorganic complexes. Counterion effects

Cited by 7 publications

References 11 publications

Redox control of ferrocene-based complexes with systematically extended π-conjugated connectors: switchable and tailorable second order nonlinear optics

Redox control of ferrocene-based complexes with systematically extended π-conjugated connectors: switchable and tailorable second order nonlinear optics

Computational Study of Polarizabilities and Second Hyperpolarizabilities of Inorganic Transition Metal Thiometalates and Metalates in Solution

Relativistic Effects on Magnetic Resonance Parameters and Other Properties of Inorganic Molecules and Metal Complexes

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