MO-HEOM: Extending Hierarchical Equations of Motion to Molecular Orbital Space
Fuente:
arXiv
Guardado en:
| Autores principales: | , , |
|---|---|
| Formato: | Preprint |
| Publicado: |
2025
|
| Materias: | |
| Acceso en línea: | |
| Etiquetas: |
Agregar Etiqueta
Sin Etiquetas, Sea el primero en etiquetar este registro!
|
| _version_ | 1866912793133842432 |
|---|---|
| author | Zhang, Yankai Tanimura, Yoshitaka Hirata, So |
| author_facet | Zhang, Yankai Tanimura, Yoshitaka Hirata, So |
| contents | Studies of quantum thermal effects on molecular excitation dynamics have often relied on oversimplified models, such as energy eigenstates or low-dimensional potentials, which fail to capture the complexity of real chemical systems. In reality, molecules are spatially extended and embedded in anisotropic environments, where molecular orbitals (MOs) play a central role in determining quantum behavior. To advance beyond these limitations, we propose a three-dimensional rotationally invariant system-bath (3D-RISB) model within the MO framework, with explicit inclusion of intramolecular vibrational motion. From this MO foundation, we derive numerically ``exact'' hierarchical equations of motion (MO-HEOM). As a demonstration, we analyze hydrogen molecules and hydrogen molecular ions with vibrational degrees of freedom, revealing their linear absorption spectra. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2512_22962 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | MO-HEOM: Extending Hierarchical Equations of Motion to Molecular Orbital Space Zhang, Yankai Tanimura, Yoshitaka Hirata, So Chemical Physics Statistical Mechanics Studies of quantum thermal effects on molecular excitation dynamics have often relied on oversimplified models, such as energy eigenstates or low-dimensional potentials, which fail to capture the complexity of real chemical systems. In reality, molecules are spatially extended and embedded in anisotropic environments, where molecular orbitals (MOs) play a central role in determining quantum behavior. To advance beyond these limitations, we propose a three-dimensional rotationally invariant system-bath (3D-RISB) model within the MO framework, with explicit inclusion of intramolecular vibrational motion. From this MO foundation, we derive numerically ``exact'' hierarchical equations of motion (MO-HEOM). As a demonstration, we analyze hydrogen molecules and hydrogen molecular ions with vibrational degrees of freedom, revealing their linear absorption spectra. |
| title | MO-HEOM: Extending Hierarchical Equations of Motion to Molecular Orbital Space |
| topic | Chemical Physics Statistical Mechanics |
| url | https://arxiv.org/abs/2512.22962 |