N-Representability Violations in Truncated Equation-of-Motion Coupled-Cluster Methods

التفاصيل البيبلوغرافية
العنوان: N-Representability Violations in Truncated Equation-of-Motion Coupled-Cluster Methods
المؤلفون: Yuwono, Stephen H., DePrince III, A. Eugene
سنة النشر: 2023
المجموعة: Physics (Other)
مصطلحات موضوعية: Physics - Chemical Physics
الوصف: One-electron reduced density matrices (1RDMs) from equation-of-motion (EOM) coupled-cluster with single and double excitations (CCSD) calculations are analyzed to assess their N-representability ({\em i.e.}, whether they are derivable from an physical N-electron state). We identify EOM-CCSD stationary states whose 1RDMs violate either ensemble-state N-representability conditions or pure-state conditions known as generalized Pauli constraints (GPCs). As such, these 1RDMs do not correspond to any physical N-electron state. Unphysical states are also encountered in the course of time-dependent EOM-CC simulations; when an external field drives transitions between a pair of stationary states with pure-state N-representable 1RDMs, the 1RDM of the time-dependent state can violate ensemble-state conditions. These observations point to potential challenges in interpreting the results of time-dependent EOM-CCSD simulations.
نوع الوثيقة: Working Paper
URL الوصول: http://arxiv.org/abs/2305.06457
رقم الأكسشن: edsarx.2305.06457
قاعدة البيانات: arXiv