A1 Journal article (refereed)
Addressing Dynamics at Catalytic Heterogeneous Interfaces with DFT-MD : Anomalous Temperature Distributions from Commonly Used Thermostats (2022)

Korpelin, V., Kiljunen, T., Melander, M. M., Caro, M. A., Kristoffersen, H. H., Mammen, N., Apaja, V., & Honkala, K. (2022). Addressing Dynamics at Catalytic Heterogeneous Interfaces with DFT-MD : Anomalous Temperature Distributions from Commonly Used Thermostats. Journal of Physical Chemistry Letters, 13(11), 2644-2652. https://doi.org/10.1021/acs.jpclett.2c00230

JYU authors or editors

Publication details

All authors or editors: Korpelin, Ville; Kiljunen, Toni; Melander, Marko M.; Caro, Miguel A.; Kristoffersen, Henrik H.; Mammen, Nisha; Apaja, Vesa; Honkala, Karoliina

Journal or series: Journal of Physical Chemistry Letters

ISSN: 1948-7185

eISSN: 1948-7185

Publication year: 2022

Publication date: 17/03/2022

Volume: 13

Issue number: 11

Pages range: 2644-2652

Publisher: American Chemical Society (ACS)

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1021/acs.jpclett.2c00230

Publication open access: Openly available

Publication channel open access: Partially open access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/80252


Density functional theory-based molecular dynamics (DFT-MD) has been widely used for studying the chemistry of heterogeneous interfacial systems under operational conditions. We report frequently overlooked errors in thermostated or constant-temperature DFT-MD simulations applied to study (electro)catalytic chemistry. Our results demonstrate that commonly used thermostats such as Nose−Hoover, Berendsen, and simple velocity rescaling methods fail to provide are liable temperature description for systems considered. Instead, nonconstant temperatures and large temperature gradients within the different parts of the system are observed. The errors are not a “feature” of any particular code but a represent in several ab initio molecular dynamics implementations. This uneven temperature distribution, due to inadequate thermostatting, is well-known in the classical MD community, where it is ascribed to the failure in kinetic energy equipartition among different degrees of freedom in heterogeneous systems (Harvey et al. J. Comput. Chem. 1998, 726−740) and termed the flying ice cube effect. We provide tantamount evidence that interfacial systems are susceptible to substantial flying ice cube effects and demonstrate that the traditional Nose−Hoover and Berendsen thermostats should be applied with care when simulating, for example, catalytic properties or structures of solvated interfaces and supported clusters. We conclude that the flying ice cube effect in these systems can be conveniently avoided using Langevin dynamics.

Keywords: chemistry; temperature regulators; density functional theory; molecular dynamics

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Ministry reporting: Yes

Reporting Year: 2022

Preliminary JUFO rating: 3

Last updated on 2022-20-09 at 13:23