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Spin state and open-shell character dependences of the static second hyperpolarizability (γ) are theoretically investigated using hydrogen chain models H2n(1≤n≤3) at the full configuration interaction level of approximation. The variation in γ is examined as a function of changing the spin state for a variety of open-shell characters ranging from the closed-shell to pure open-shell states. It is found that (i) in the nearly ground-state closed-shell region, higher-spin states exhibit much larger γ values than the singlet state; (ii) in the intermediate and large open-shell character regions, the singlet state presents the largest γ and γ decreases with the spin multiplicity; and (iii) in the pure open-shell region, all the spin states exhibit negligible γ values. The summation-over-states approach enables rationalizing these findings by considering the primarily contributing excited states. These results reveal that there are two types of molecular design guidelines for enhancing γ values: (a) for nearly closed-shell systems, increasing the spin multiplicity; and (b) for open-shell singlet systems, tuning the open-shell character to the intermediate region.
|Journal||Physical Review A - Atomic, Molecular, and Optical Physics|
|Publication status||Published - 28 Oct 2016|
- quantum chemistry
- spin state
- open-shell character
- second hyperpolarisabillity
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1/04/14 → 31/12/21
Functional Supramolecular Systems (IUAP No. P7/5) – Modeling the nonlinear optical properties of functionalized surfaced and complex systems
NENON, S. & CHAMPAGNE, B.
1/06/12 → 31/12/13