Issue 11, 2024

Discovery of excellent ultraviolet nonlinear optical materials in chlorates and bromates with highly stereochemically active lone pairs

Abstract

The discovery of short-wave ultraviolet (SWUV, λPM < 266 nm, PM = phase-matching) and deep ultraviolet (DUV, λPM < 200 nm) nonlinear optical (NLO) crystals is urgently required and full of challenges. Unlike the conventional strategy of using π-conjugated groups (such as BO3) as core motifs for constructing UV NLO crystals, herein the long-neglected stereochemically active lone pair (SCALP) groups ClO3 and BrO3 are innovatively proposed to be good UV NLO functional motifs based on the group property prediction, and the NLO performance of chlorates and bromates has been investigated systematically for the first time by first-principles methods. Benefiting from the high polarizability of ClO3 and BrO3 and their favorable alignments, the halate crystals AClO3 and ABrO3 (A = NH4, K, Rb and Cs) exhibit high SHG coefficients comparable to that of classical β-BaB2O4 (4.2–4.8 × KDP for AClO3 and 6.1–7.1 × KDP for ABrO3). Meanwhile, their wide band gaps and large optical anisotropy lead to very short λPM deep into DUV and SWUV (185–195 nm for AClO3 and 210–220 nm for ABrO3). Remarkably, ABrO3 shows a rare full-wavelength phase-matching capability. Hence AClO3 and ABrO3 could be promising DUV and SWUV NLO candidates, respectively, and the UV NLO potential of ClO3 and BrO3 is further demonstrated by profound mechanism analysis. This work opens up a new avenue for the development of SWUV and even DUV NLO materials.

Graphical abstract: Discovery of excellent ultraviolet nonlinear optical materials in chlorates and bromates with highly stereochemically active lone pairs

Supplementary files

Article information

Article type
Research Article
Submitted
20 Feb 2024
Accepted
26 Mar 2024
First published
27 Mar 2024

Inorg. Chem. Front., 2024,11, 3150-3158

Discovery of excellent ultraviolet nonlinear optical materials in chlorates and bromates with highly stereochemically active lone pairs

C. Hu, Q. Chen, F. Kong and J. Mao, Inorg. Chem. Front., 2024, 11, 3150 DOI: 10.1039/D4QI00462K

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements