Time-Dependent Equation-of-Motion Coupled-Cluster Simulations with a Defective Hamiltonian

التفاصيل البيبلوغرافية
العنوان: Time-Dependent Equation-of-Motion Coupled-Cluster Simulations with a Defective Hamiltonian
المؤلفون: Yuwono, Stephen H., Cooper, Brandon C., Zhang, Tianyuan, Li, Xiaosong, DePrince III, A. Eugene
سنة النشر: 2023
المجموعة: Physics (Other)
مصطلحات موضوعية: Physics - Chemical Physics
الوصف: Simulations of laser-induced electron dynamics in a molecular system are performed using time-dependent (TD) equation-of-motion (EOM) coupled-cluster (CC) theory. The target system has been chosen to highlight potential shortcomings of truncated TD-EOM-CC methods [represented in this work by TD-EOM-CC with single and double excitations (TD-EOM-CCSD)], where unphysical spectroscopic features can emerge. Specifically, we explore driven resonant electronic excitations in magnesium fluoride in the proximity of an avoided crossing. Near the avoided crossing, the CCSD similarity-transformed Hamiltonian is defective, meaning that it has complex eigenvalues, and oscillator strengths may take on negative values. When an external field is applied to drive transitions to states exhibiting these traits, unphysical dynamics are observed. For example, the stationary states that make up the time-dependent state acquire populations that can be negative, exceed one, or even be complex-valued.
نوع الوثيقة: Working Paper
DOI: 10.1063/5.0157852
URL الوصول: http://arxiv.org/abs/2305.06412
رقم الأكسشن: edsarx.2305.06412
قاعدة البيانات: arXiv