Intervalley Excitonic Hybridization, Optical Selection Rules, and Imperfect Circular Dichroism in Monolayer h-BN

• Published in: Physical review letters 2022-01, Vol.128 (4), p.047402-047402, Article 047402
• Main Authors: Zhang, Fang, Ong, Chin Shen, Ruan, Jia Wei, Wu, Meng, Shi, Xing Qiang, Tang, Zi Kang, Louie, Steven G
• Format: Article
• Language: English
• ISSN: 0031-9007; 1079-7114
• DOI: 10.1103/PhysRevLett.128.047402

We perform first-principles GW plus Bethe-Salpeter equation calculations to investigate the photophysics of monolayer hexagonal boron nitride (h-BN), revealing excitons with novel k-space characteristics. The excitonic states forming the first and third peaks in its absorption spectrum are s-like, but those of the second peak are notably p-like, a first finding of strong co-occurrence of bright s-like and bright p-like states in an intrinsic 2D material. Moreover, even though the k-space wave function of these excitonic states are centered at the K and K^{'} valleys as in monolayer transition metal dichalcogenides, the k-space envelope functions of the basis excitons at one valley have significant extents to the basin of the other valley. As a consequence, the optical response of monolayer h-BN exhibits a lack of circular dichroism, as well as a coupling that induces an intervalley mixing between s- and p-like states.