التفاصيل البيبلوغرافية
| العنوان: |
Multistate, Polarizable QM/MM Embedding Scheme Based on the Direct Reaction Field Method: Solvatochromic Shifts, Analytical Gradients and Optimizations of Conical Intersections in Solution |
| المؤلفون: |
Alexander Humeniuk, William J. Glover |
| سنة النشر: |
2024 |
| المجموعة: |
Smithsonian Institution: Figshare |
| مصطلحات موضوعية: |
Biophysics, Biochemistry, Biotechnology, Plant Biology, Space Science, Chemical Sciences not elsewhere classified, Physical Sciences not elsewhere classified, static polarizability leads, nonadiabatic coupling vectors, essentially quantitative levels, effective core potentials, construct analytical gradients, polarizable solvent shell, two excited states, analytical gradients, excited states, solvent shifts, nonpolar solvent, transfer states, electronic states, system calculations, state crossings, solvatochromic shifts, single hamiltonian, recently introduced, polarizable qm, pauli repulsion, older implementations, negligible shifts, n < |
| الوصف: |
We recently introduced a polarizable embedding scheme based on an integral-exact reformulation of the direct reaction field method (IEDRF) that accounts for the differential solvation of ground and excited states in QM/MM simulations. The polarization and dispersion interactions between the quantum-mechanical (QM) and molecular-mechanical (MM) regions are described by the DRF Hamiltonian, while the Pauli repulsion between explicitly treated QM electrons and the implicit electron density around MM atoms is modeled with effective core potentials. A single Hamiltonian is used for all electronic states so that Born–Oppenheimer states belonging to the same geometry are orthogonal and state crossings are well-defined. In this work, we describe the implementation of the method using graphical processing unit acceleration in TeraChem, where it is combined with multiple electronic structure methods, including Hartree–Fock, time-dependent density functional theory, and complete active space self-consistent field. In contrast with older implementations of the DRF method, integrals of the polarization operators are evaluated exactly. Expressions for ingredients needed to construct analytical gradients and nonadiabatic coupling vectors are derived and tested by optimizing a conical intersection between two excited states in the presence of a polarizable solvent shell. The method is applied to estimate the solvent shifts of absorption energies of a series of donor–acceptor dyes having low-lying charge-transfer states. Even for a nonpolar solvent such as n -hexane, the inclusion of its static polarizability leads to non-negligible shifts that improve the agreement to essentially quantitative levels (0.03 eV) with full-system calculations. Good agreement with the positions of the experimental absorption maxima measured in solution is also observed. |
| نوع الوثيقة: |
dataset |
| اللغة: |
unknown |
| Relation: |
https://figshare.com/articles/dataset/Multistate_Polarizable_QM_MM_Embedding_Scheme_Based_on_the_Direct_Reaction_Field_Method_Solvatochromic_Shifts_Analytical_Gradients_and_Optimizations_of_Conical_Intersections_in_Solution/25193914 |
| DOI: |
10.1021/acs.jctc.3c01018.s003 |
| الاتاحة: |
https://doi.org/10.1021/acs.jctc.3c01018.s003 |
| Rights: |
CC BY-NC 4.0 |
| رقم الانضمام: |
edsbas.9F136E92 |
| قاعدة البيانات: |
BASE |