A theoretical study of the hyperpolarisabilities of nickel dithiolene molecules

Craig, B.I.; Williams, G.R.J.

doi:10.1002/amo.860010503

Cited by 5 publications

(1 citation statement)

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“…[13][14][15][16][17] However, there are only few theoretical studies on the NLO properties of Ni dithiolenes. 12,[18][19][20] In this work we will first study the electronic structure of NiBDT employing a series of methods: CASSCF/CASPT2, ab initio VB, and DFT. Each one of them provides some distinct piece of information and all of them contribute to complete the puzzle of the electronic structure of NiBDT.…”

Section: Introductionmentioning

confidence: 99%

Linear and nonlinear optical properties of a series of Ni-dithiolene derivatives

Serrano‐Andrés

Avramopoulos

Li³

et al. 2009

The Journal of Chemical Physics

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Some linear and nonlinear optical (NLO) properties of Ni(SCH)(4) and several of its derivatives have been computed by employing a series of basis sets and a hierarchy of methods (e.g., HF, DFT, coupled cluster, and multiconfigurational techniques). The electronic structure of Ni(SCH)(4) has been also analyzed by using CASSCF/CASPT2, ab initio valence bond, and DFT methods. In particular we discuss how the diradicaloid character (DC) of Ni(SCH)(4) significantly affects its NLO properties. The quasidegeneracy of the two lowest-energy singlet states 1 (1)A(g) and 1 (1)B(1u), the clear DC nature of the former, and the very large number of low-lying states enhance the NLO properties values. These particular features are used to interpret the NLO properties of Ni(SCH)(4). The DC of the considered derivatives has been estimated and correlated with the NLO properties. CASVB computations have shown that the structures with Ni(II) are the dominant ones, while those with Ni(0) and Ni(IV) have negligible weight. The weights of the four diradical structures were discussed in connection with the weight of the structures, where all the electrons are paired. Comparative discussion of the properties of Ni(SCH)(4) with those of tetrathia fulvalene demonstrates the very large effect of Ni on the properties of the Ni-dithiolene derivatives. A similar remarkable effect on the NLO properties is produced by one or two methyl or C(3)S groups. The considered Ni-dithiolene derivatives have exceptionally large NLO properties. This feature in connection with their other physical properties makes them ideal candidates for photonic applications.

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