The important role of superalkalis on the static first hyperpolarizabilities of new electrides: Theoretical investigation on superalkali-doped hexamethylenetetramine (HMT)

- The HMT−X, HMT−FX2, and HMT−OX3 (X = Li, Na, and K) compounds possess electride characteristics.
- The (super)alkali atoms interaction induces the HOMO-LUMO gap of the HMT.
- These electride moleculars exhibit considerably large static first hyperpolarizabilities.

On the basis of Hexamethylenetetramine (HMT), a new class of (super)alkali-doped electrides HMT−X, HMT−FX2, and HMT−OX3 (X = Li, Na, and K) were designed in theory. The results reveal that superalkali FX2 and OX3 can keep their structural integrity in these studied compounds. These electrides possess significantly large first hyperpolarizabilities (β0) in the range of 0.65 × 103-4.72 × 105 au due to diffuse excess electrons from chemical doping. It is found that the superalkali effect on the β0 value is more significant than that of simple alkali doping. Furthermore, employing the heavier superalkali (FK2 and OK3) can dramatically enhance the β0 values of the HMT−FK2 and HMT−OK3. The further investigations show that small transition energies is the decisive factor for the large β0 values of (super)alkali-doped electrides. The ratios between the vibrational and electronic contributions on (hyper)polarizability demonstrate that the vibrational contributions play an important role in determining the static (hyper)polarizabilities. This paper not only designs novel electrides with large NLO response but also expands the application range of superalkali cluster.

101