A Direct Diabatic States Construction Method with Consistent Orbitals for Valence and Rydberg States

TL;DR

The paper introduces DDSC, a new method for constructing diabatic states using fragment wavefunctions and orbitals, enabling accurate modeling of valence and Rydberg states and diabatic couplings.

Contribution

It presents a novel DDSC methodology that constructs all diabatic states at once using fragment-localized orbitals, improving accuracy and efficiency for charge transfer systems.

Findings

Successfully applied to LiH molecule

Constructs both valence and Rydberg diabatic states

Enables direct computation of diabatic couplings

Abstract

This work presents a novel methodology termed Direct Diabatic States Construction (DDSC), which integrates fragment wavefunctions into an anti-symmetric wavefunction for the entire system. Using a fragment-localized state-consistent molecular orbital (FL-SC MO), this approach enables direct construction of all diabatic states at the same root. Each diabatic state is formed as a linear combination of a set of diabatic configurations. The validity and effectiveness of DDSC have been demonstrated through its application to the LiH molecule. The results show that this method is suitable for constructing both valence and Rydberg diabatic states. One of the key advantages of DDSC is its ability to directly compute diabatic couplings, which can be converted to non-adiabatic coupling (NAC) vectors along the reaction coordinate. The DDSC method efficiently builds the diabatic potential energy matrix (DPEM), especially for systems with clear fragment partitions and weak inter-fragment interactions, such as charge transfer reactions.