Generalized Formulation of the Density Functional Tight Binding-Based Restricted Ensemble Kohn-Sham Method with Onsite Correction to Long-Range Correction.
In Seong LeeSeung Kyu MinPublished in: Journal of chemical theory and computation (2022)
We present a generalized formulation for the combination of the density functional tight binding (DFTB) approach and the state-interaction state-average spin-restricted ensemble-referenced Kohn-Sham (SI-SA-REKS or SSR) method by considering onsite correction (OC) as well as the long-range corrected (LC) functional. The OC contribution provides more accurate energies and analytic gradients for individual microstates, while the multireference character of the SSR provides the correct description for conical intersections. We benchmark the LC-OC-DFTB/SSR method against various DFTB calculation methods for excitation energies and conical intersection structures with π/π* or n /π* characters. Furthermore, we perform excited-state molecular dynamics simulations with a molecular rotary motor with variations of LC-OC-DFTB/SSR approaches. We show that the OC contribution to the LC functional is crucial to obtain the correct geometry of conical intersections.
Keyphrases
- density functional theory
- molecular dynamics simulations
- simultaneous determination
- mass spectrometry
- drug delivery
- blood brain barrier
- genetic diversity
- high resolution
- liquid chromatography
- molecular dynamics
- room temperature
- single molecule
- clinical trial
- convolutional neural network
- molecular docking
- solid phase extraction
- machine learning
- high resolution mass spectrometry