Zhang Yang, Su Peifeng, Lasorne Benjamin, Braïda Benoît, Wu Wei
The State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, and College of Chemistry and Chemical Engineering,, Xiamen University, Xiamen, Fujian 361005, China.
ICGM, Univ Montpellier, CNRS, ENSCM, Montpellier, France.
J Phys Chem Lett. 2020 Jul 2;11(13):5295-5301. doi: 10.1021/acs.jpclett.0c01466. Epub 2020 Jun 19.
A novel valence-bond-based automatic diabatization method by compression, called valence-bond-based compression approach for dibatization (VBCAD), is presented in this Letter. It is a "black-box" type method that provides an automatic diabatization from a classical valence bond (VB) perspective. In VBCAD, a model space projection is performed by an eigenvalue decomposition algorithm followed by dimensional reduction based on a sequence of Householder transformations. Our diabaticity criterion is implemented in a way that maximizes the diversity of VB structure weights between different diabatic states. Owing to the rigorous Householder transformations employed in this entire procedure, the invariance of the target eigensubspace is preserved. This is illustrated on two prototypical examples.
