TY - JOUR
T1 - Generalized Nuclear-Electronic Orbital Multistate Density Functional Theory for Multiple Proton Transfer Processes
AU - Dickinson, Joseph A.
AU - Yu, Qi
AU - Hammes-Schiffer, Sharon
N1 - Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/7/6
Y1 - 2023/7/6
N2 - Proton transfer and hydrogen tunneling play pivotal roles in many chemical and biological processes. The nuclear-electronic orbital multistate density functional theory (NEO-MSDFT) approach was developed to describe hydrogen tunneling systems within the multicomponent NEO framework, where the transferring proton is quantized and treated with molecular orbital techniques on the same level as the electrons. Herein, the NEO-MSDFT framework is generalized to an arbitrary number of quantum protons to allow applications to systems involving the transfer and tunneling of multiple protons. The generalized NEO-MSDFT approach is shown to produce delocalized, bilobal proton densities and accurate tunneling splittings for fixed geometries of the formic acid dimer and asymmetric substituted variants, as well as the porphycene molecule. Investigation of a protonated water chain highlights the applicability of this approach to proton relay systems. This work provides the foundation for nuclear-electronic quantum dynamics simulations of a wide range of multiple proton transfer processes.
AB - Proton transfer and hydrogen tunneling play pivotal roles in many chemical and biological processes. The nuclear-electronic orbital multistate density functional theory (NEO-MSDFT) approach was developed to describe hydrogen tunneling systems within the multicomponent NEO framework, where the transferring proton is quantized and treated with molecular orbital techniques on the same level as the electrons. Herein, the NEO-MSDFT framework is generalized to an arbitrary number of quantum protons to allow applications to systems involving the transfer and tunneling of multiple protons. The generalized NEO-MSDFT approach is shown to produce delocalized, bilobal proton densities and accurate tunneling splittings for fixed geometries of the formic acid dimer and asymmetric substituted variants, as well as the porphycene molecule. Investigation of a protonated water chain highlights the applicability of this approach to proton relay systems. This work provides the foundation for nuclear-electronic quantum dynamics simulations of a wide range of multiple proton transfer processes.
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U2 - 10.1021/acs.jpclett.3c01422
DO - 10.1021/acs.jpclett.3c01422
M3 - Article
C2 - 37379485
AN - SCOPUS:85164238375
SN - 1948-7185
VL - 14
SP - 6170
EP - 6178
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 26
ER -