Solvent Induced Proton Polarization within the Nuclear−Electronic Orbital Framework

Lambros, Eleftherios; Link, Benjamin; Chow, Mathew; Hammes‐Schiffer, Sharon; Li, Xiaosong

doi:10.1021/acs.jpclett.3c00471

Cited by 5 publications

(10 citation statements)

References 49 publications

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“…Moreover, the O···O (or O···N) and O···H distances are observed to be slightly shorter when the hydrogen-bonded proton is quantized with the NEO approach, which is discussed further below. The distances between the hydrogen-bonded proton and its bonded oxygen (or nitrogen), HO (or HN), are slightly elongated due to solvation, consistent with previous findings . For the systems studied herein, the distance changes indicate that solvation can strengthen the hydrogen bond.…”

Section: Resultssupporting

confidence: 90%

“…The distances between the hydrogen-bonded proton and its bonded oxygen (or nitrogen), H�O (or H�N), are slightly elongated due to solvation, consistent with previous findings. 17 For the systems studied herein, the distance changes indicate that solvation can strengthen the hydrogen bond. Furthermore, we found that the hydrogen-bond angle is similar for both conventional DFT and NEO-DFT calculations.…”

Section: ■ Results and Discussionmentioning

confidence: 86%

“…The exploration of coupled nuclear–electronic dynamics is an especially promising direction within the NEO framework, as exemplified by the NEO real-time time-dependent density functional theory (RT-TDDFT) method and NEO-Ehrenfest dynamics approach . Recently, implicit solvation effects have been included in NEO calculations , through the polarizable continuum model (PCM). , This NEO-PCM approach has been applied to a variety of chemical systems and has been used to simulate the dynamics of an excited-state intramolecular proton transfer reaction in solution …”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Nuclear–Electronic Orbital QM/MM Approach: Geometry Optimizations and Molecular Dynamics

Chow

Lambros

et al. 2023

J. Chem. Theory Comput.

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Hybrid quantum mechanical/molecular mechanical (QM/MM) methods allow simulations of chemical reactions in atomistic solvent and heterogeneous environments such as proteins. Herein, the nuclear–electronic orbital (NEO) QM/MM approach is introduced to enable the quantization of specified nuclei, typically protons, in the QM region using a method such as NEO-density functional theory (NEO-DFT). This approach includes proton delocalization, polarization, anharmonicity, and zero-point energy in geometry optimizations and dynamics. Expressions for the energies and analytical gradients associated with the NEO-QM/MM method, as well as the previously developed polarizable continuum model (NEO-PCM), are provided. Geometry optimizations of small organic molecules hydrogen bonded to water in either dielectric continuum solvent or explicit atomistic solvent illustrate that aqueous solvation can strengthen hydrogen-bonding interactions for the systems studied, as indicated by shorter intermolecular distances at the hydrogen-bond interface. We then performed a real-time direct dynamics simulation of a phenol molecule in explicit water using the NEO-QM/MM method. These developments and initial examples provide the foundation for future studies of nuclear–electronic quantum dynamics in complex chemical and biological environments.

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Section: Resultssupporting

confidence: 90%

Section: ■ Results and Discussionmentioning

confidence: 86%

Section: Introductionmentioning

confidence: 99%

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Nuclear–Electronic Orbital QM/MM Approach: Geometry Optimizations and Molecular Dynamics

Chow

Lambros

et al. 2023

J. Chem. Theory Comput.

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“…In addition, linear scaling can be achieved with an efficient implementation of this model, which could be promising for the application to large chemical and biological systems of practical interest in the future. In this work, we apply CNEO–ddCOSMO to investigate the anomalous solvatochromic shift of C–H stretch frequency of the formate ion, which was not fully understood by previous theoretical investigations. , Although the C–H vibrational frequency in the solution can be correctly predicted by NEO-PCM, , the large solvatochromic shift is not recovered.…”

Section: Introductionmentioning

confidence: 92%

“…In this work, we apply CNEO−ddCOSMO to investigate the anomalous solvatochromic shift of C−H stretch frequency of the formate ion, 33 which was not fully understood by previous theoretical investigations. 34,35 Although the C−H vibrational frequency in the solution can be correctly predicted by NEO-PCM, 35,36 the large solvatochromic shift is not recovered.…”

Section: ■ Introductionmentioning

confidence: 99%

Constrained Nuclear-Electronic Orbital Density Functional Theory with a Dielectric Continuum Solvent Model

2023

J. Phys. Chem. A

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Solvent effects are crucial for simulating chemical and biological processes in solutions. The continuum solvation model is widely used for incorporating solvent effects with different levels of theoretical descriptions of solutes. For solutes and solutions containing hydrogen atoms, nuclear quantum effects can also be nonnegligible for reliable simulations. In this work, we couple our recently developed constrained nuclear-electronic orbital density functional theory with a dielectric continuum solvation model to cover nuclear quantum effects and solvent effects simultaneously. This approach is applied to the formate ion, where an anomalous solvatochromic shift in C–H stretch frequency was reported in experiments. By using this new approach to account for nuclear quantum effects and solvent effects, we show that the vibrational frequency of the C–H stretch and the solvatochromic shift are accurately described.

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Electrolyte Effects in Electrocatalytic Kinetics^†

Li,

Zhang,

Zhuang

et al. 2024

Chin. J. Chem.

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Comprehensive SummaryTuning electrolyte properties is a widely recognized strategy to enhance activity and selectivity in electrocatalysis, drawing increasing attention in this domain. Despite extensive experimental and theoretical studies, debates persist about how various electrolyte components influence electrocatalytic reactions. We offer a concise review focusing on current discussions, especially the contentious roles of cations. This article further examines how different factors affect the interfacial solvent structure, particularly the hydrogen‐bonding network, and delves into the microscopic kinetics of electron and proton‐coupled electron transfer. We also discuss the overarching influence of solvents from a kinetic modeling perspective, aiming to develop a robust correlation between electrolyte structure and reactivity. Lastly, we summarize ongoing research challenges and suggest potential directions for future studies on electrolyte effects in electrocatalysis. Key ScientistsIn 1956, Marcus theory was developed to describe the mechanism of outer‐sphere electron transfer (OS‐ET). In 1992, Nocera et al. directly measured proton‐coupled electron transfer (PCET) kinetics for the first time, and their subsequent research in 1995 investigated the effects of proton motion on electron transfer (ET) kinetics. In 1999 and 2000, Hammes‐schiffer et al. developed the multistate continuum theory for multiple charge reactions and deduced the rate expressions for nonadiabatic PCET reactions in solution, laying the theoretical foundation for the analysis of PCET kinetics in electrochemical processes. In 2006, Saveant et al. verified the concerted proton and electron transfer (CPET) mechanism in the oxidation of phenols coupled with intramolecular amine‐driven proton transfer (PT). Their subsequent work in 2008 reported the pH‐dependent pathways of electrochemical oxidation of phenols.Electrolyte effects in electrocatalysis have gained emphasis in recent years. In 2009, Markovic's pioneering work proposed non‐covalent interactions between hydrated alkaline cations and adsorbed OH species in oxygen reduction reaction (ORR)/hydrogen oxidation reaction (HOR). In 2011, Markovic et al. significantly enhanced hydrogen evolution reaction (HER) activity in alkaline solution by improving water dissociation, which was assumed to dominate the sluggish HER kinetics in such media. In comparation, Yan et al. applied hydrogen binding energy (HBE) theory in 2015 to explain the pH‐dependent HER/HOR activity. Cations play a significant role in regulating the selectivity and activity of carbon dioxide reduction (CO2RR). In 2016 and 2017, Karen Chan et al. introduced the electric field generated by solvated cations to explain the cation effects on electrochemical CO2RR. Conversely, in 2021, Koper et al. suggested that short‐range electrostatic interactions between partially desolvated metal cations and CO2 stabilized CO2 and promoted CO2RR.Recent researches have combined the exploration of the electrical double layer (EDL) structure with theoretical analysis of PCET kinetics. In 2019, Huang et al. developed a microscopic Hamiltonian model to quantitatively understand the sluggish hydrogen electrocatalysis in alkaline media. In 2021, two meticulous studies from Shao‐Horn's group analyzed the effects of cations on reorganization energy and the impacts of hydrogen bonds between proton donors and acceptors on proton tunneling kinetics, respectively. Electrolyte effects on proton transport process were researched in recent years. In 2022, Hu et al. and Chen et al. proposed that the cation‐induced electric field distribution and pH‐dependent hydrogen bonding network connectivity played essential roles in proton transport, separately.

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Solvent Induced Proton Polarization within the Nuclear−Electronic Orbital Framework

Cited by 5 publications

References 49 publications

Nuclear–Electronic Orbital QM/MM Approach: Geometry Optimizations and Molecular Dynamics

Nuclear–Electronic Orbital QM/MM Approach: Geometry Optimizations and Molecular Dynamics

Constrained Nuclear-Electronic Orbital Density Functional Theory with a Dielectric Continuum Solvent Model

Electrolyte Effects in Electrocatalytic Kinetics^†

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Solvent Induced Proton Polarization within the Nuclear−Electronic Orbital Framework

Cited by 5 publications

References 49 publications

Nuclear–Electronic Orbital QM/MM Approach: Geometry Optimizations and Molecular Dynamics

Nuclear–Electronic Orbital QM/MM Approach: Geometry Optimizations and Molecular Dynamics

Constrained Nuclear-Electronic Orbital Density Functional Theory with a Dielectric Continuum Solvent Model

Electrolyte Effects in Electrocatalytic Kinetics†

Contact Info

Product

Resources

About

Electrolyte Effects in Electrocatalytic Kinetics^†