Report
Understanding the Cavity Born-Oppenheimer Approximation
| العنوان: | Understanding the Cavity Born-Oppenheimer Approximation |
|---|---|
| المؤلفون: | Fiechter, Marit R., Richardson, Jeremy O. |
| سنة النشر: | 2024 |
| المجموعة: | Physics (Other) Quantum Physics |
| مصطلحات موضوعية: | Physics - Chemical Physics, Quantum Physics |
| الوصف: | Experiments have demonstrated that vibrational strong coupling between molecular vibrations and light modes can significantly change molecular properties, such as ground-state reactivity. Theoretical studies towards the origin of this exciting observation can roughly be divided in two categories, with studies based on Hamiltonians that simply couple a molecule to a cavity mode via its ground-state dipole moment on the one hand, and on the other hand ab initio calculations that self-consistently include the effect of the cavity mode on the electronic ground state within the cavity Born-Oppenheimer (CBO) approximation; these approaches are not equivalent. The CBO approach is more rigorous, but unfortunately it requires the rewriting of electronic-structure code, and gives little physical insight. In this work, we exploit the relation between the two approaches and demonstrate on a real molecule (hydrogen fluoride) that for realistic coupling strengths, we can recover CBO energies and spectra to high accuracy using only out-of-cavity quantities from standard electronic-structure calculations. In doing so, we discover what the physical effects underlying the CBO results are. Our methodology can aid in incorporating more, possibly important features in models, play a pivotal role in demystifying CBO results and provide a practical and efficient alternative to full CBO calculations. |
| نوع الوثيقة: | Working Paper |
| URL الوصول: | http://arxiv.org/abs/2401.03532 |
| رقم الانضمام: | edsarx.2401.03532 |
| قاعدة البيانات: | arXiv |
| الوصف غير متاح. |