Biorthonormal Formalism for Nonadiabatic Coupled Cluster Dynamics
| Autor: | Eirik F. Kjønstad, Henrik Koch |
|---|---|
| Přispěvatelé: | Kjønstad, Eirik F., Koch, Henrik |
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Physics
Left and right 010304 chemical physics Observable 01 natural sciences Full configuration interaction Article Computer Science Applications Schrödinger equation Vibronic coupling symbols.namesake Coupled cluster Classical mechanics 0103 physical sciences symbols Orthonormal basis Physical and Theoretical Chemistry Wave function Settore CHIM/02 - Chimica Fisica |
| Zdroj: | Journal of Chemical Theory and Computation |
| Popis: | In coupled cluster theory, the electronic states are biorthonormal in the sense that the left states are orthonormal to the right states. Here, we present an extension of this formalism to a left and right total molecular wave function. Starting from left and right Born-Huang expansions, we derive projected Schrödinger equations for the left and right nuclear wave functions. Observables may be extracted from the resulting wave function pair using standard expressions. The formalism is shown to be invariant under electronic basis transformations, such as normalization of the electronic states. Consequently, the nonadiabatic coupling elements can be expressed with biorthonormal electronic wave functions. Calculating normalization factors that scale as full configuration interaction is not necessary, contrary to claims in the literature. For nonadiabatic nuclear dynamics, we need expressions for the derivative couplings in the biorthonormal formalism. These are derived in a Lagrangian framework. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|