We present efficient analytical gradients of property-based diabatic states and couplings using a Lagrangian formalism. Unlike previous formulations, the method achieves a computational scaling that is independent of the number of adiabatic states used to construct the diabats. The approach is generalizable to other property-based diabatization schemes and electronic structure methods as long as analytical energy gradients are available and integral derivatives with the property operator can be formed. We also introduce a scheme to phase and reorder diabats to ensure their continuity between molecular configurations. We demonstrate this for the specific case of Boys diabatic states obtained from state-averaged complete active space self-consistent field electronic structure calculations with GPU acceleration in the TeraChem package. The method is used to test the Condon approximation for the hole transfer in an explicitly solvated model DNA oligomer.
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http://dx.doi.org/10.1063/5.0142590 | DOI Listing |
J Phys Chem A
January 2025
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
We revisit the naked transition metal cation (Ti) and methanol reaction and go beyond the standard Landau-Zener (LZ) picture when modeling the intersystem crossing (ISC) rate between the lowest doublet and quartet states. We use both (i) unconstrained Born-Oppenheimer molecular dynamics (BOMD) calculations with an approximate two-state method to estimate population transfer between spin diabats and (ii) constrained dynamics to explore energetically accessible portions of the - 1 crossing seam, where is the total number of internal degrees of freedom. Whereas previous LZ calculations (that necessarily relied on the Condon approximation to be valid) fell short and predicted much slower crossing probabilities than shown in experiment, we show that ISC can occur rapidly because the spin-orbit coupling (SOC) between the doublet and quartet surfaces can vary by 2 orders of magnitude (depending on where in the seam the crossing occurs during dynamics) and the crossing region is revisited multiple times during a dynamics run of a few hundred femtoseconds.
View Article and Find Full Text PDFJ Phys Chem A
December 2024
Department of Chemistry, Indian Institute of Technology Patna, Bihta 801106, India.
This study probes the vibronic interactions in the photoelectron spectra of CAlGe, exploring its six excited electronic states through an approach that combines the electronic structure calculations and the quantum nuclear dynamics. Central to this investigation is utilizing a model diabatic Hamiltonian, which allows for the exact evaluation of Hamiltonian parameters and fitting potential energy cuts (PECs). Notably, the analysis of these PECs uncovers pronounced nonadiabatic effects within the photoelectron spectra, emphasized by the presence of multiple conical intersections.
View Article and Find Full Text PDFPhys Chem Chem Phys
December 2024
School of Energy and Power Engineering, Shandong University, Jinan, 250061, People's Republic of China.
CH is one of the most spectroscopically studied diatomic molecules. The rovibronic spectra of the methylidyne radical (CH) in adiabatic and diabatic representations are obtained based on data, including 12 potential energy curves, 38 dipole moment curves, 79 spin-orbit coupling curves, and 18 electronic angular momentum coupling curves. We employed the internally contracted multireference configuration interaction method including the Davidson correction with the aug-cc-pV(5+d)Z basis set for the C atom and the aug-cc-pV5Z basis set for the H atom.
View Article and Find Full Text PDFJ Chem Theory Comput
December 2024
State Key Laboratory for Mesoscopic Physics and Collaborative Innovation Center of Quantum Matter, School of Physics, Peking University, Beijing 100871, China.
The Jahn-Teller (JT) effect, as a spontaneous symmetry-breaking mechanism arising from the coupling between electronic and nuclear degrees of freedom, is a widespread phenomenon in molecular and condensed matter systems. Here, we investigate the influence of the JT effect on the photodissociation dynamics of CFI molecules. Based on ab initio calculation, we obtain the three-dimensional potential energy surfaces for and states and establish a diabatic Hamiltonian model to study the wavepacket dynamics in the CFI photodissociation process.
View Article and Find Full Text PDFPhys Chem Chem Phys
December 2024
School of Chemistry, University of Hyderabad, Hyderabad 500 046, India.
The hydrogen exchange reaction, H + H → H + H, along with its isotopic variants, has been the cornerstone for the development of new and novel dynamical mechanisms of gas-phase bimolecular reactions since the 1930s. The dynamics of this reaction are theoretically investigated in this work to elucidate the effect of reagent vibrational excitation on differential cross sections (DCSs) in a nonadiabatic situation. The dynamical calculations are carried out using a time-dependent quantum mechanical method, both on the lower adiabatic potential energy surface and employing a two-state coupled diabatic theoretical model to explicitly include all the nonadiabatic couplings present in the 1E' ground electronic manifold of the H system.
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