Brady, Ryan P;
Drury, Charlie;
Yurchenko, Sergei N;
Tennyson, Jonathan;
(2024)
Numerical Equivalence of Diabatic and Adiabatic Representations in Diatomic Molecules.
Journal of Chemical Theory and Computation
10.1021/acs.jctc.3c01150.
(In press).
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Abstract
The (time-independent) Schrödinger equation for atomistic systems is solved by using the adiabatic potential energy curves (PECs) and the associated adiabatic approximation. In cases where interactions between electronic states become important, the associated nonadiabatic effects are taken into account via derivative couplings (DDRs), also known as nonadiabatic couplings (NACs). For diatomic molecules, the corresponding PECs in the adiabatic representation are characterized by avoided crossings. The alternative to the adiabatic approach is the diabatic representation obtained via a unitary transformation of the adiabatic states by minimizing the DDRs. For diatomics, the diabatic representation has zero DDR and nondiagonal diabatic couplings ensue. The two representations are fully equivalent and so should be the rovibronic energies and wave functions, which result from the solution of the corresponding Schrödinger equations. We demonstrate (for the first time) the numerical equivalence between the adiabatic and diabatic rovibronic calculations of diatomic molecules using the ab initio curves of yttrium oxide (YO) and carbon monohydride (CH) as examples of two-state systems, where YO is characterized by a strong NAC, while CH has a strong diabatic coupling. Rovibronic energies and wave functions are computed using a new diabatic module implemented in the variational rovibronic code DUO. We show that it is important to include both the diagonal Born−Oppenheimer correction and nondiagonal DDRs. We also show that the convergence of the vibronic energy calculations can strongly depend on the representation of nuclear motion used and that no one representation is best in all cases.
| Type: | Article |
|---|---|
| Title: | Numerical Equivalence of Diabatic and Adiabatic Representations in Diatomic Molecules |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1021/acs.jctc.3c01150 |
| Publisher version: | http://dx.doi.org/10.1021/acs.jctc.3c01150 |
| Language: | English |
| Additional information: | This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third-party material in this article are included in the Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy |
| URI: | https://discovery-pp.ucl.ac.uk/id/eprint/10185025 |
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