@article{66553, abstract = {{Stimulated by the renewed interest and recent developments in semiempirical quantum chemical (SQC) methods for noncovalent interactions, we examine the properties of liquid water under ambient conditions by means of molecular dynamics (MD) simulations, both with the conventional neglect of diatomic differential overlap-type methods, e.g., AM1 and PM6, and with DFTB-type (density-functional tight-binding) methods, e.g., DFTB2 and GFN-xTB (Geometry-Frequency-Noncovalent eXtended Tight-Binding). Besides the original parameter sets, some specifically reparameterized SQC methods (denoted as AM1-W, PM6-fm, and DFTB2-iBi) targeting various smaller water systems ranging from molecular clusters to bulk are considered as well. The quality of these different SQC methods for describing liquid water properties under ambient conditions is assessed by comparison with well-established experimental data and also with BLYP-D3 density functional theory-based ab initio MD simulations. Our analyses reveal that static and dynamic properties of bulk water are poorly described by all considered SQC methods with the original parameters, regardless of the underlying theoretical models, with most of the methods suffering from too weak hydrogen bonds and hence predicting a far too fluid water with highly distorted hydrogen bond kinetics. Meanwhile, the reparameterized force-matched PM6-fm method is shown to be able to quantitatively reproduce the static and dynamic features of liquid water and thus can be used as a computationally efficient alternative to electronic structure-based MD simulations for liquid water that requires extended length and time scales. DFTB2-iBi predicts a slightly overstructured water with reduced fluidity, whereas AM1-W gives an amorphous ice-like structure for water under ambient conditions.}}, author = {{Wu, Xin and Elgabarty, Hossam and Alizadeh, Vahideh and Henao, Andrés and Zysk, Frederik and Plessl, Christian and Ehlert, Sebastian and Hutter, Jürg and Kühne, Thomas D.}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, number = {{3}}, publisher = {{AIP Publishing}}, title = {{{Benchmarking semiempirical quantum chemical methods on liquid water}}}, doi = {{10.1063/5.0343753}}, volume = {{165}}, year = {{2026}}, } @article{62034, abstract = {{Effective single-particle theories, such as Hartree–Fock, density functional theory, and tight-binding, are limited by the computational cost of the self-consistent field (SCF) procedure, which typically scales cubically with the system size. This makes large-scale applications impractical without specialized algorithms and hardware. Here, we present the submatrix and graphical processing unit (GPU)-accelerated software implementation of the PTB tight-binding potential, realized in the open-source ptb codebase [M. Mueller, A. Katbashev, and S. Ehlert (2025). “grimme-lab/ptb: v3.8.1,” Zenodo. https://zenodo.org/records/17015872]. We first benchmark a traditional diagonalization-based SCF solver against density-matrix-based purification approaches, systematically varying both system size and computer hardware. Our findings show that the usage of GPUs permits shifting the boundaries to much larger systems than previously thought feasible, achieving an overall 10–15-fold performance speedup. Second, we introduce the implementation of a decomposition-type submatrix method, specifically designed for efficient operation on mid- to large-sized systems, to address the computational overhead associated with full-system diagonalization. We demonstrate that, from a certain dimension (≈104 basis functions) on, our submatrix method reduces the overall computational cost while maintaining acceptable numerical accuracy. Our study demonstrates the significance of the interplay between modern hardware, algorithmic considerations, and novel tight-binding methods, paving the way for further development in this direction.}}, author = {{Katbashev, Abylay and Schade, Robert and Laß, Michael and Müller, Marcel and Grimme, Stefan and Hansen, Andreas and Kühne, Thomas}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, number = {{13}}, publisher = {{AIP Publishing}}, title = {{{Submatrix and GPU-accelerated implementation of density matrix tight-binding}}}, doi = {{10.1063/5.0271379}}, volume = {{163}}, year = {{2025}}, } @article{23611, author = {{Steinrück, Hans-Georg}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, pages = {{174703}}, title = {{{Modeling cyclic voltammetry during solid electrolyte interphase formation: Baseline scenario of a dynamically evolving tunneling barrier resulting from a homogeneous single-phase insulating film}}}, doi = {{10.1063/5.0049591}}, volume = {{154}}, year = {{2021}}, } @article{33648, author = {{Ghasemi, Alireza and Kühne, Thomas}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, keywords = {{Physical and Theoretical Chemistry, General Physics and Astronomy}}, number = {{7}}, publisher = {{AIP Publishing}}, title = {{{Artificial neural networks for the kinetic energy functional of non-interacting fermions}}}, doi = {{10.1063/5.0037319}}, volume = {{154}}, year = {{2021}}, } @article{19501, author = {{Zhao, Bin and Manthe, Uwe}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, keywords = {{pc2-ressources}}, title = {{{Non-adiabatic transitions in the reaction of fluorine with methane}}}, doi = {{10.1063/5.0013852}}, year = {{2020}}, } @article{17386, author = {{Kühne, Thomas D. and Iannuzzi, Marcella and Del Ben, Mauro and Rybkin, Vladimir V. and Seewald, Patrick and Stein, Frederick and Laino, Teodoro and Khaliullin, Rustam Z. and Schütt, Ole and Schiffmann, Florian and al., et}}, issn = {{1089-7690}}, journal = {{The Journal of Chemical Physics}}, number = {{19}}, pages = {{194103}}, publisher = {{AIP Publishing}}, title = {{{CP2K: An electronic structure and molecular dynamics software package - Quickstep: Efficient and accurate electronic structure calculations}}}, doi = {{10.1063/5.0007045}}, volume = {{152}}, year = {{2020}}, } @article{23618, author = {{Steinrück, Hans-Georg and Cao, Chuntian and Veith, Gabriel M. and Toney, Michael F.}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, pages = {{084702}}, title = {{{Toward quantifying capacity losses due to solid electrolyte interphase evolution in silicon thin film batteries}}}, doi = {{10.1063/1.5142643}}, volume = {{152}}, year = {{2020}}, } @article{16956, author = {{Chatwell, René Spencer and Vrabec, Jadran}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, keywords = {{pc2-ressources}}, title = {{{Bulk viscosity of liquid noble gases}}}, doi = {{10.1063/1.5142364}}, year = {{2020}}, } @article{41028, author = {{Naumova, Maria A. and Kalinko, Aleksandr and Wong, Joanne W. L. and Alvarez Gutierrez, Sol and Meng, Jie and Liang, Mingli and Abdellah, Mohamed and Geng, Huifang and Lin, Weihua and Kubicek, Katharina and Biednov, Mykola and Lima, Frederico and Galler, Andreas and Zalden, Peter and Checchia, Stefano and Mante, Pierre-Adrien and Zimara, Jennifer and Schwarzer, Dirk and Demeshko, Serhiy and Murzin, Vadim and Gosztola, David and Jarenmark, Martin and Zhang, Jianxin and Bauer, Matthias and Lawson Daku, Max Latevi and Khakhulin, Dmitry and Gawelda, Wojciech and Bressler, Christian and Meyer, Franc and Zheng, Kaibo and Canton, Sophie E.}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, keywords = {{Physical and Theoretical Chemistry, General Physics and Astronomy}}, number = {{21}}, publisher = {{AIP Publishing}}, title = {{{Exploring the light-induced dynamics in solvated metallogrid complexes with femtosecond pulses across the electromagnetic spectrum}}}, doi = {{10.1063/1.5138641}}, volume = {{152}}, year = {{2020}}, } @article{21944, author = {{Nüske, Feliks and Boninsegna, Lorenzo and Clementi, Cecilia}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, title = {{{Coarse-graining molecular systems by spectral matching}}}, doi = {{10.1063/1.5100131}}, year = {{2019}}, } @article{16955, author = {{Heinen, Matthias and Vrabec, Jadran}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, keywords = {{pc2-ressources}}, title = {{{Evaporation sampled by stationary molecular dynamics simulation}}}, doi = {{10.1063/1.5111759}}, year = {{2019}}, } @article{21942, author = {{Boninsegna, Lorenzo and Nüske, Feliks and Clementi, Cecilia}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, title = {{{Sparse learning of stochastic dynamical equations}}}, doi = {{10.1063/1.5018409}}, year = {{2018}}, } @article{21943, author = {{Hruska, Eugen and Abella, Jayvee R. and Nüske, Feliks and Kavraki, Lydia E. and Clementi, Cecilia}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, title = {{{Quantitative comparison of adaptive sampling methods for protein dynamics}}}, doi = {{10.1063/1.5053582}}, year = {{2018}}, } @article{41834, author = {{Hansch, Markus and Hämisch, Benjamin and Schweins, Ralf and Prévost, Sylvain and Huber, Klaus}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, keywords = {{Physical and Theoretical Chemistry, General Physics and Astronomy}}, number = {{1}}, publisher = {{AIP Publishing}}, title = {{{Liquid-liquid phase separation in dilute solutions of poly(styrene sulfonate) with multivalent cations: Phase diagrams, chain morphology, and impact of temperature}}}, doi = {{10.1063/1.5006618}}, volume = {{148}}, year = {{2018}}, } @article{41832, author = {{Urbanski, Anna and Hansch, Markus and Lopez, Carlos G. and Schweins, Ralf and Hertle, Yvonne and Hellweg, Thomas and Polzer, Frank and Huber, Klaus}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, keywords = {{Physical and Theoretical Chemistry, General Physics and Astronomy}}, number = {{16}}, publisher = {{AIP Publishing}}, title = {{{Polyacrylates in the presence of an extraordinary monovalent cation—Solution behavior and metal nanoparticle formation}}}, doi = {{10.1063/1.5028182}}, volume = {{149}}, year = {{2018}}, } @article{41833, author = {{Hansch, Markus and Kaub, Hans Peter and Deck, Sascha and Carl, Nico and Huber, Klaus}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, keywords = {{Physical and Theoretical Chemistry, General Physics and Astronomy}}, number = {{11}}, publisher = {{AIP Publishing}}, title = {{{Reaction enthalpy from the binding of multivalent cations to anionic polyelectrolytes in dilute solutions}}}, doi = {{10.1063/1.5019877}}, volume = {{148}}, year = {{2018}}, } @article{21938, author = {{Nüske, Feliks and Wu, Hao and Prinz, Jan-Hendrik and Wehmeyer, Christoph and Clementi, Cecilia and Noé, Frank}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, title = {{{Markov state models from short non-equilibrium simulations—Analysis and correction of estimation bias}}}, doi = {{10.1063/1.4976518}}, year = {{2017}}, } @article{21939, author = {{Wu, Hao and Nüske, Feliks and Paul, Fabian and Klus, Stefan and Koltai, Péter and Noé, Frank}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, title = {{{Variational Koopman models: Slow collective variables and molecular kinetics from short off-equilibrium simulations}}}, doi = {{10.1063/1.4979344}}, year = {{2017}}, } @article{21937, author = {{Nüske, Feliks and Schneider, Reinhold and Vitalini, Francesca and Noé, Frank}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, title = {{{Variational tensor approach for approximating the rare-event kinetics of macromolecular systems}}}, doi = {{10.1063/1.4940774}}, year = {{2016}}, } @article{10035, author = {{Li, Yanlu and Sanna, Simone and Schmidt, Wolf Gero}}, issn = {{0021-9606}}, journal = {{The Journal of Chemical Physics}}, title = {{{Modeling intrinsic defects in LiNbO3 within the Slater-Janak transition state model}}}, doi = {{10.1063/1.4883737}}, year = {{2014}}, }