Perspectives of geminal methods for large molecular systems

Abstract

Geminals are counterparts of two‐electron chemical bonds and lone pairs in the realm of wave functions. Antisymmetrized products of geminals provide a solid framework for studies of electron pairing in molecular systems. Natural advantages of geminal wave functions such as the correct description of bond breaking and formation make them a powerful model for electronic structure calculations. The concerted efforts to develop geminal‐based methods concentrate on increasing their accuracy and universality. The downside is the high computational cost limiting applications to small and toy systems. In contrast, the inherent local structure of optimal geminals opens pathways to development of methods for large systems. In particular, perspectives for linear scaling and hybrid quantum/classical approaches using geminals are discussed. The same principles are proposed for development of computational schemes for covalently bound and molecular crystals. © 2015 Wiley Periodicals, Inc.