22 results on '"Hanning Chen"'
Search Results
2. Fe–Fe Double-Atom Catalysts for Murine Coronavirus Disinfection: Nonradical Activation of Peroxides and Mechanisms of Virus Inactivation
- Author
-
Zhe Zhou, Mengqiao Li, Yuxin Zhang, Lingchen Kong, Virginia F. Smith, Mengyang Zhang, Anders J. Gulbrandson, Gordon H. Waller, Feng Lin, Xitong Liu, David P. Durkin, Hanning Chen, and Danmeng Shuai
- Subjects
Environmental Chemistry ,General Chemistry - Published
- 2023
3. Transformation of Graphitic Carbon Nitride by Reactive Chlorine Species: 'Weak' Oxidants Are the Main Players
- Author
-
Mengqiao Li, David P. Durkin, Gordon Waller, Yaochun Yu, Yujie Men, Tao Ye, Hanning Chen, and Danmeng Shuai
- Subjects
Environmental Chemistry ,General Chemistry - Published
- 2023
4. Temperature-Dependent Recombination of Triplet Biexcitons in Singlet Fission of Hexacene
- Author
-
Yuqin Qian, Zhi-Chao Huang-Fu, Tong Zhang, Xia Li, Avetik R. Harutyunyan, Gugang Chen, Hanning Chen, and Yi Rao
- Subjects
General Energy ,Physical and Theoretical Chemistry ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials - Published
- 2022
5. Herzberg–Teller Effect in Single-Crystalline Hexacene at Finite Temperatures
- Author
-
Yuqin Qian, Tong Zhang, Xia Li, Yi Rao, and Hanning Chen
- Subjects
General Energy ,Physical and Theoretical Chemistry ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials - Published
- 2022
6. Radical-Driven Decomposition of Graphitic Carbon Nitride Nanosheets: Light Exposure Matters
- Author
-
David P. Durkin, Dairong Liu, Michael J. Wagner, Hanning Chen, Nan Jiang, Hongchen Shen, Danmeng Shuai, Kevin R. McKenzie, Zhihong Yin, Xue Li, Ashlee Aiello, Mengqiao Li, and Xing Chen
- Subjects
Chemistry ,Graphitic carbon nitride ,General Chemistry ,Activation energy ,Photochemistry ,Decomposition ,Nanostructures ,Nanomaterials ,chemistry.chemical_compound ,Photocatalysis ,Environmental Chemistry ,Degradation (geology) ,Graphite ,Hydroxyl radical ,Nitrogen Compounds ,Nanosheet - Abstract
Understanding the transformation of graphitic carbon nitride (g-C3N4) is essential to assess nanomaterial robustness and environmental risks. Using an integrated experimental and simulation approach, our work has demonstrated that the photoinduced hole (h+) on g-C3N4 nanosheets significantly enhances nanomaterial decomposition under •OH attack. Two g-C3N4 nanosheet samples D and M2 were synthesized, among which M2 had more pores, defects, and edges, and they were subjected to treatments with •OH alone and both •OH and h+. Both D and M2 were oxidized and released nitrate and soluble organic fragments, and M2 was more susceptible to oxidation. Particularly, h+ increased the nitrate release rate by 3.37-6.33 times even though the steady-state concentration of •OH was similar. Molecular simulations highlighted that •OH only attacked a limited number of edge-site heptazines on g-C3N4 nanosheets and resulted in peripheral etching and slow degradation, whereas h+ decreased the activation energy barrier of C-N bond breaking between heptazines, shifted the degradation pathway to bulk fragmentation, and thus led to much faster degradation. This discovery not only sheds light on the unique environmental transformation of emerging photoreactive nanomaterials but also provides guidelines for designing robust nanomaterials for engineering applications.
- Published
- 2021
7. Symmetry-Breaking Enhanced Herzberg–Teller Effect with Brominated Polyacenes
- Author
-
Tong Zhang, Yuqin Qian, Jian Han, Yi Rao, Avetik R. Harutyunyan, Hanning Chen, and Gugang Chen
- Subjects
010304 chemical physics ,010402 general chemistry ,01 natural sciences ,Hexacene ,Molecular physics ,Molecular electronic transition ,0104 chemical sciences ,chemistry.chemical_compound ,Vibronic coupling ,Tetracene ,chemistry ,Normal mode ,0103 physical sciences ,Molecular symmetry ,Symmetry breaking ,Physics::Chemical Physics ,Physical and Theoretical Chemistry ,Wave function - Abstract
Molecular symmetry is vital to the selection rule of vibrationally resolved electronic transition, particularly when the nuclear dependence of electronic wave function is explicitly treated by including Franck-Condon (FC) factor, Franck-Condon/Herzberg-Teller (FC/HT) interference, and Herzberg-Teller (HT) coupling. Our present study investigated the light absorption spectra of highly symmetric tetracene, pentacene, and hexacene molecules of point-group D2h, as well as their monobrominated derivatives with a lower Cs symmetry. It was found that the symmetry-breaking monobromination allows more vibrational normal modes and their pairs to contribute to FC/HT interference and HT coupling, respectively. Through a projection of a molecule's vibrational normal modes to its irreducible representations, a linear relationship between the FC/HT intensity to the polyacene's size was deduced alongside a quadratic dependence of the HT intensity. Both theoretically derived correlations were well justified by our numerical simulations, which also demonstrated an approximately 20% improvement on the agreement with experimental line shape if the HT theory is adopted to replace the FC approximation. Moreover, for these low-symmetry monobrominated polyacenes, the FC intensity was even weaker than its FC/HT and HT counterparts at some excitation energies, making the HT theory imperative to decipher vibronic coupling, a fundamental driving force behind numerous chemical, biological, and photophysical processes.
- Published
- 2021
8. Singlet Fission Driven by Anisotropic Vibronic Coupling in Single-Crystalline Pentacene
- Author
-
Tong Zhang, Gang-Hua Deng, Xia Li, Hanning Chen, Wei Jiang, Yuqin Qian, Yi Rao, Gugang Chen, and Avetik R. Harutyunyan
- Subjects
Materials science ,Phonon ,Fission ,Exciton ,Ab initio ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Molecular physics ,0104 chemical sciences ,Pentacene ,Condensed Matter::Materials Science ,Vibronic coupling ,chemistry.chemical_compound ,chemistry ,Singlet fission ,Ultrafast laser spectroscopy ,Physics::Atomic and Molecular Clusters ,Condensed Matter::Strongly Correlated Electrons ,General Materials Science ,Physics::Chemical Physics ,Physical and Theoretical Chemistry ,0210 nano-technology - Abstract
Vibronic coupling is believed to play an important role in siglet fission, wherein a photoexcited singlet exciton is converted into two triplet excitons. In the present study, we examine the role of vibronic coupling in singlet fission using polarized transient absorption microscopy and ab initio simulations on single-crystalline pentacene. It was found that singlet fission in pentacene is greatly facilitated by the vibrational coherence of a 35.0 cm-1 phonon, where anisotropic coherence persists extensively for a few picoseconds. This coherence-preserving phonon that drives the anisotropic singlet fission is made possible by a unique cross-axial charge-transfer intermediate state. In the same fashion, this phonon was also found to predominantly drive the quantum decohence of a correlated triplet pair to form a decoupled triplet dimer. Moreover, our transient kinetic experimental data illustrates notable directional anisotropicity of the singlet fission rate in single-crystalline pentacene.
- Published
- 2021
9. Herzberg–Teller Effect on the Vibrationally Resolved Absorption Spectra of Single-Crystalline Pentacene at Finite Temperatures
- Author
-
Yuqin Qian, Hanning Chen, Avetik R. Harutyunyan, Yi Rao, Gugang Chen, and Xia Li
- Subjects
010304 chemical physics ,Absorption spectroscopy ,010402 general chemistry ,01 natural sciences ,Molecular physics ,Molecular electronic transition ,0104 chemical sciences ,Pentacene ,chemistry.chemical_compound ,Vibronic coupling ,chemistry ,Normal mode ,Atomic electron transition ,0103 physical sciences ,Vibronic spectroscopy ,Density functional theory ,Physics::Chemical Physics ,Physical and Theoretical Chemistry - Abstract
The line shape of an electronic spectrum conveys the coupling between electronic and vibrational degrees of freedom. In the present study, the light absorption spectra of single-crystalline pentacene were measured by polarized UV-vis microscopy at 77, 185, and 293 K. The vibronic coupling encoded in each spectrum was resolved by the Herzberg-Teller theory that considers the contributions from the Franck-Condon (FC) factor, Franck-Condo/Herzberg-Teller (FC/HT) interference, and Herzberg-Teller (HT) coupling. Specifically, excitation energies, electronic transition dipole moments, and their nuclear gradients were evaluated by the GW method to ensure numerical accuracy, while the computationally efficient density function theory was employed to determine the optimized structures and vibrational normal modes. For every pair of electronic transition and normal mode that gives rise to a strong vibronic transition intensity, we examined their spatial characteristics by projecting them onto the three crystal axes. It was found that all normal modes strongly coupled to the lowest-lying a-polarized electronic transitions oscillate along axis a, whereas none of their counterparts for the lowest-lying b-polarized electronic transitions is predominantly along axis b. This notable difference on the alignment between the electronic transition and molecular vibration could help the directional control of charge dissociation and/or spin separation. Moreover, a significant variance of the destructive FC/HT interference was discovered with increasing temperatures that can well explain the a-polarized fading tableland near 650 nm. Finally, the importance of HT coupling was corroborated by comparing its intensity with those of FC factor and FC/HT interference. Taken all together, the vibrational dependence of the electronic wave function is critical to resolve the light absorption spectra of single-crystalline pentacene and its temperature effects, facilitating the systematic design of functional optical materials based on pentacene and its derivatives.
- Published
- 2020
10. Effect of Surface Roughness on Electrochemical Adsorption/Desorption of Dopamine by Carbonaceous Electrodes
- Author
-
Hanning Chen and Alexander G. Zestos
- Abstract
Electrochemical adsorption/desorption of dopamine by carbonaceous electrodes upon voltage variation is the key process of neurotransmitter detection through fast scan cyclic voltammetry. In the present study, ab initio molecular dynamics simulation empowered by image-charge method was applied to calculate the adsorption/desorption free energy profile of dopamine and dopamine o-quinone at fixed electrode potentials using our newly developed open-source CP2K simulation package. It was found that the activation barriers for both adsorption and desorption were substantially reduced with increasing surface roughness of the carbonaceous electrodes. For example, on the flat graphene electrode, the activation barrier for dopamine adsorption at V0=−0.4V is 1.34 kcal/mol, while its counterpart on the curved nanotube electrode drops to 0.82 kcal/mol. Moreover, the diffusion coefficient of dopamine decreases by approximately 60% when it is moving close to the graphene electrode, while its diffusion is accelerated by up to 100% when the nanotube electrode is adopted. The faster diffusion alongside the reduced activation barrier greatly facilitates the electrochemically driven adsorption/desorption of dopamine by nanotube electrodes, in consistent with experimental findings that a rougher carbonaceous surface is critical for fast scan cyclic voltammetry.
- Published
- 2021
11. Dual Binding Configurations of Subphthalocyanine on Ag(100) Substrate Characterized by Scanning Tunneling Microscopy, Tip-Enhanced Raman Spectroscopy, and Density Functional Theory
- Author
-
Jeremy F. Schultz, Philip J. Whiteman, Hanning Chen, Nan Jiang, and Zachary D. Porach
- Subjects
Materials science ,Molecular binding ,02 engineering and technology ,Substrate (electronics) ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,law.invention ,symbols.namesake ,General Energy ,law ,Chemical physics ,symbols ,Molecule ,Density functional theory ,Physical and Theoretical Chemistry ,Scanning tunneling microscope ,0210 nano-technology ,Raman spectroscopy ,Superstructure (condensed matter) ,Excitation - Abstract
In order to fully characterize interfacial systems at the smallest scales, advanced analytical surface techniques have to be employed to render a complete picture of molecular assemblies. In this study, we carried out ultrahigh vacuum (UHV) scanning tunneling microscopy (STM) experiments on subphthalocyanine (SubPc) molecules, which are self-assembled on a Ag(100) substrate. The UHV STM experiments were complemented by tip-enhanced Raman spectroscopy (TERS), surface-enhanced Raman spectroscopy (SERS), and density functional theory (DFT) calculations. The TERS spectrum shows a high signal intensity (>600 ADU·mW–1·s–1) due to piezo-driven in-vacuo excitation and collection lenses with large numerical apertures (NA = 0.4). A new two-dimensional molecular superstructure of SubPc was discovered to consist of two distinct molecular binding configurations, both of which interact relatively weakly with the underlying metallic substrate as revealed by high-signal-to-noise enhanced Raman spectra. Our results demons...
- Published
- 2018
12. Computer Simulation of Singlet Fission in Single Crystalline Pentacene by Functional Mode Vibronic Theory
- Author
-
Justin E. Elenewski, Hanning Chen, Ulyana Cubeta, and Edward Ko
- Subjects
Coupling ,Chemistry ,Diabatic ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Transition rate matrix ,01 natural sciences ,Molecular physics ,0104 chemical sciences ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,Multiple exciton generation ,Pentacene ,Superposition principle ,chemistry.chemical_compound ,General Energy ,Singlet fission ,Physical and Theoretical Chemistry ,Atomic physics ,0210 nano-technology ,Mixing (physics) - Abstract
We have applied our functional mode framework for singlet fission to pentacene, a prototypical organic material for multiple exciton generation. It was found that singlet fission in pentacene occurs predominantly through a coherent process mediated by a virtual charge-transfer (CT) intermediate, which lies slightly above the photoexcited S1S0 state. This energetic near-degeneracy facilitates a substantial vibronic superposition, leading to a rapid transition rate of 25.1 ps–1. By contrast, the direct S1S0 → T1T1 path constitutes a much more sluggish route with a rate of 2.6 ps–1, largely due to the weak diabatic coupling between participant states. These data collectively afford an experimentally consistent rate of 27.7 ps–1 for the entire singlet fission process. The presence of this low-lying CT intermediate suggests that enhanced electronic coupling between S1S0 and T1T1 states may collude with coherent vibrational mixing to expedite the formation of triplet pairs. The knowledge gleaned from our invest...
- Published
- 2017
13. Functional Mode Singlet Fission Theory
- Author
-
Justin E. Elenewski, Hanning Chen, Ulyana Cubeta, and Edward Ko
- Subjects
Chemistry ,Intermolecular force ,Diabatic ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,Reaction coordinate ,Multiple exciton generation ,General Energy ,Thermodynamic limit ,Singlet fission ,Molecular orbital ,Density functional theory ,Physical and Theoretical Chemistry ,Atomic physics ,0210 nano-technology - Abstract
Singlet fission is a multiple exciton generation process that splits a singlet exciton (S0S1) into a correlated triplet pair (T1T1), affording a route to overcome the long-standing Shockley–Queisser thermodynamic limit for solar energy conversion. A new theory, based on multiconfiguration-constrained density functional theory and functional mode analysis, has been developed to model intermolecular singlet fission in organic photovoltaics. Specifically, constrained density functional theory is first employed to construct molecular orbitals for the six spin configurations comprising T1T1, the diabatic product state. In a subsequent step, linear response time-dependent density functional theory is utilized to formulate the S0S1 diabatic reactant state. Functional mode analysis is then applied to a thermalized ensemble of diabatic energy gaps to ascertain the reaction coordinate for the S0S1 → T1T1 transition. If singlet fission is assumed to follow a direct route, its rate may be evaluated using a modified J...
- Published
- 2017
14. Functional Mode Hot Electron Transfer Theory
- Author
-
Jesse Y. Cai, Hanning Chen, Justin E. Elenewski, and Wei Jiang
- Subjects
Thermal equilibrium ,Chemistry ,02 engineering and technology ,Photon energy ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Hot band ,0104 chemical sciences ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,General Energy ,Excited state ,Molecule ,Charge carrier ,Physics::Chemical Physics ,Physical and Theoretical Chemistry ,Atomic physics ,0210 nano-technology ,Line (formation) ,Fermi Gamma-ray Space Telescope - Abstract
Charge carriers that have been driven out of thermal equilibrium by their excessive vibrational energies are termed hot carriers. A theory has been developed to model the injection of these vibrationally excited electrons by explicitly accounting for the time-dependent thermal relaxation of the electron-transfer driving vibrational mode, as ascertained using functional mode analysis. Specifically, the thermal relaxation rate of the driving mode is first determined through the so-called frozen-phonon approach after which the energy-dependent line shape function is revisited to include memory effects for the vibrational quanta within the framework of Fermi’s golden rule. As shown by the numerical simulations of a 6-methyl-azulene-2-carboxylic acid dye molecule bound to an anatase TiO2[101] surface, our new theory not only yields persistently faster electron injection rates with higher incident photon energy but also exhibits a sharp increase when the vibrational quanta of the photoexcited dye molecule chang...
- Published
- 2016
15. QM/MM Study of Photoinduced Reduction of a Tetrahedral Ag20+ Cluster by a Ag Atom
- Author
-
George C. Schatz, Mark A. Ratner, and Hanning Chen
- Subjects
Chemistry ,Point particle ,Solvation ,Photoinduced electron transfer ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,QM/MM ,Electron transfer ,General Energy ,Ionization ,Density functional theory ,Physics::Chemical Physics ,Physical and Theoretical Chemistry ,Atomic physics ,Excitation - Abstract
A hybrid quantum mechanics/classical mechanics (QM/MM) approach was developed to investigate photoinduced electron transfer (PIET) from a neutral Ag atom to an ionized tetrahedral Ag20+ cluster, both of which are solvated in water. In this approach, PIET was modeled as a coherent quantum process involving both vertical excitation and electron injection by our recently developed constrained real-time time-dependent density functional theory (C-RT-TDDFT) (J. Phys. Chem. C 2011, 115, 18810), whereas the aqueous solvation structure for the (Ag–Ag20)+ complex was determined by the empirical flexible simple point charge (SPC/Fw) force field (J. Chem. Phys. 2006, 124, 024503). An electrostatic embedding scheme was chosen to accurately represent the mutual polarization between the QM subsystem (the (Ag–Ag20)+ complex) and the MM subsystem (water molecules) in a self-adaptive manner that turns out to be critical to the relative stability of the electron transfer diabatic states in addition to their electronic coup...
- Published
- 2012
16. Computational Modeling of Plasmon-Enhanced Light Absorption in a Multicomponent Dye Sensitized Solar Cell
- Author
-
Martin G. Blaber, Joseph T. Hupp, George C. Schatz, Mark A. Ratner, Stacey D. Standridge, Hanning Chen, and Erica J. DeMarco
- Subjects
Nanostructure ,Chemistry ,Nanotechnology ,Molecular physics ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,law.invention ,Dye-sensitized solar cell ,Wavelength ,General Energy ,law ,Extinction (optical mineralogy) ,Solar cell ,Density functional theory ,Physical and Theoretical Chemistry ,Absorption (electromagnetic radiation) ,Plasmon - Abstract
Plasmon-enhanced light absorption in a multicomponent Ag/Ag2O/TiO2/N3 dye-sensitized solar cell (DSSC) core–shell nanostructure is studied using a hybrid quantum mechanics/classical electrodynamics (QM/ED) methodology in which the Ag/Ag2O/TiO2 nanostructure is treated by the finite-difference time-domain method and the N3 dye is treated by real-time time-dependent density functional theory. As part of this modeling, the undetermined thickness of the nonplasmonic Ag2O layer on the Ag/Ag2O/TiO2 particle was estimated by comparing the computed plasmon wavelength with experimental results. Also, absorption cross sections for the N3 dye were calculated for different locations of the dye on the TiO2 surface. The spatially averaged absorption cross sections for different thicknesses of TiO2 were evaluated and used to estimate the relative incident photon conversion efficiency. Encouragingly, it is found that the QM/ED calculations can well reproduce the factor of ∼10 experimental extinction difference spectrum a...
- Published
- 2012
17. Time-Dependent Theory of the Rate of Photo-induced Electron Transfer
- Author
-
George C. Schatz, Mark A. Ratner, and Hanning Chen
- Subjects
Chemistry ,Diabatic ,Photoinduced electron transfer ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,Marcus theory ,Photoexcitation ,symbols.namesake ,Electron transfer ,General Energy ,symbols ,Density functional theory ,Physics::Chemical Physics ,Physical and Theoretical Chemistry ,Atomic physics ,Hamiltonian (quantum mechanics) ,Ground state - Abstract
A novel approach based on constrained real-time time-dependent density functional theory (C-RT-TDDFT) is introduced to accurately evaluate the electronic Hamiltonian coupling associated with photoinduced electron transfer (PIET) using diabatic states that are defined using constrained DFT (C-DFT). In combination with the semiclassical Marcus theory, the photoexcited ET rate for coherently coupled photoexcitation and electron transfer is determined for a given incident wavelength by combining this Hamiltonian coupling with free energy changes and ground state reorganization energies that are obtained using an implicit solvation model. As an application of this method, we consider PIET for the (Ag20–Ag)+ complex as a model of a plasmon-enhanced electron transfer process. Using solar radiation intensity, the fastest PIET rate is found to be induced by an incident wavelength that is distinct (blue-shifted) from the wavelength of strongest plasmon-like excitation associated with the Ag20+ cluster, particularly...
- Published
- 2011
18. Atomistic Simulation and Measurement of pH Dependent Cancer Therapeutic Interactions with Nanodiamond Carrier
- Author
-
Jessica Lee, Robert Lam, George C. Schatz, Daniel J. Schaffer, Wing Kam Liu, Amanda S. Barnard, Dean Ho, Ashfaq Adnan, and Hanning Chen
- Subjects
Antibiotics, Antineoplastic ,Chemistry ,Pharmaceutical Science ,Nanoparticle ,Hydrogen-Ion Concentration ,Molecular Dynamics Simulation ,Nanodiamonds ,Nanostructures ,Solvent ,Molecular dynamics ,Drug Delivery Systems ,Adsorption ,Doxorubicin ,Neoplasms ,Drug Discovery ,Drug delivery ,polycyclic compounds ,Biophysics ,Humans ,Nanoparticles ,Molecular Medicine ,Molecule ,Doxorubicin Hydrochloride ,Organic chemistry ,Nanodiamond - Abstract
In this work, we have combined constant-pH molecular dynamics simulations and experiments to provide a quantitative analysis of pH dependent interactions between doxorubicin hydrochloride (DOX) cancer therapeutic and faceted nanodiamond (ND) nanoparticle carriers. Our study suggests that when a mixture of faceted ND and DOX is dissolved in a solvent, the pH of this solvent plays a controlling role in the adsorption of DOX molecules on the ND. We find that the binding of DOX molecules on ND occurs only at high pH and requires at least ∼10% of ND surface area to be fully titrated for binding to occur. As such, this study reveals important mechanistic insight underlying an ND-based pH-controlled therapeutic platform.
- Published
- 2011
19. Efficient Multistate Reactive Molecular Dynamics Approach Based on Short-Range Effective Potentials
- Author
-
Gregory A. Voth, Pu Liu, and Hanning Chen
- Subjects
Proton ,Chemistry ,Solvation ,Electrostatics ,Computer Science Applications ,Range (mathematics) ,Molecular dynamics ,symbols.namesake ,Computational chemistry ,symbols ,Statistical physics ,Physical and Theoretical Chemistry ,van der Waals force ,Order of magnitude ,Topology (chemistry) - Abstract
Nonbonded interactions between molecules usually include the van der Waals force and computationally expensive long-range electrostatic interactions. This article develops a more efficient approach: the effective-interaction multistate empirical-valence-bond (EI-MS-EVB) model. The EI-MS-EVB method relies on a mapping of all interactions onto a short-range and thus, computationally efficient effective potential. The effective potential is tabulated by matching its force to known trajectories obtained from the full-potential empirical multistate empirical-valence-bond (MS-EVB) model. The effective pairwise interaction depends on and is uniquely determined by the atomic configuration of the system, varying only with respect to the hydrogen-bonding topology. By comparing the EI-MS-EVB and full MS-EVB calculations of several equilibrium and dynamic properties important to hydrated excess proton solvation and transport, we show that the EI-MS-EVB model produces very accurate results for the specific system in which the tabulated potentials were generated. The EI-MS-EVB potential also transfers reasonably well to similar systems with different temperatures and box sizes. The EI-MS-EVB method also reduces the computational cost of the nonbonded interactions by about 1 order of magnitude in comparison with the full algorithm.
- Published
- 2010
20. Classical Electrodynamics Coupled to Quantum Mechanics for Calculation of Molecular Optical Properties: a RT-TDDFT/FDTD Approach
- Author
-
George C. Schatz, Hanning Chen, Mark A. Ratner, and Jeffrey M. McMahon
- Subjects
Physics ,Scattering ,Absorption cross section ,Finite-difference time-domain method ,Physics::Optics ,Time-dependent density functional theory ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,symbols.namesake ,General Energy ,Fourier transform ,Electric field ,Quantum mechanics ,symbols ,Classical electromagnetism ,Physics::Chemical Physics ,Physical and Theoretical Chemistry ,Local field - Abstract
A new multiscale computational methodology was developed to effectively incorporate the scattered electric field of a plasmonic nanoparticle into a quantum mechanical (QM) optical property calculation for a nearby dye molecule. For a given location of the dye molecule with respect to the nanoparticle, a frequency-dependent scattering response function was first determined by the classical electrodynamics (ED) finite-difference time-domain (FDTD) approach. Subsequently, the time-dependent scattered electric field at the dye molecule was calculated using the FDTD scattering response function through a multidimensional Fourier transform to reflect the effect of polarization of the nanoparticle on the local field at the molecule. Finally, a real-time time-dependent density function theory (RT-TDDFT) approach was employed to obtain a desired optical property (such as absorption cross section) of the dye molecule in the presence of the nanoparticle’s scattered electric field. Our hybrid QM/ED methodology was de...
- Published
- 2010
21. Unusual Hydrophobic Interactions in Acidic Aqueous Solutions
- Author
-
Gregory A. Voth, Hanning Chen, and Jianqing Xu
- Subjects
Models, Molecular ,Hofmeister series ,Hydronium ,Inorganic chemistry ,Molecular Conformation ,Sodium Chloride ,Micelle ,Hydrophobic effect ,chemistry.chemical_compound ,Molecular dynamics ,Computational chemistry ,Pentanes ,Materials Chemistry ,Computer Simulation ,Physical and Theoretical Chemistry ,Dissolution ,Aqueous solution ,Solvation ,Water ,Hydrogen-Ion Concentration ,Surfaces, Coatings and Films ,Solutions ,chemistry ,Hydrochloric Acid ,Protons ,Hydrophobic and Hydrophilic Interactions - Abstract
Hydrophobic interaction, which is believed to be a primary driving force for many fundamental chemical and biological processes such as nanostructure self-assembly, micelle formation, and protein folding, is different in acidic aqueous solutions compared to salt solutions. In this study, the aggregation/dispersion behavior of nonpolar hydrophobic molecules in aqueous solutions with varying acid (HCl) concentrations is investigated using novel molecular dynamics simulations and compared to the hydrophobic behavior in corresponding salt (NaCl) solutions. The formation of unusual weakly bound hydrophobe-hydrated proton solvation structures is observed and can be attributed to the unique "amphiphilic" characteristic of hydrated protons. This molecular-level mechanism for the acid-enhanced dissolution of hydrophobic particles also provides a novel interpretation for the apparent anomaly of the hydronium cation in the Hofmeister series.
- Published
- 2009
22. An Improved Multistate Empirical Valence Bond Model for Aqueous Proton Solvation and Transport
- Author
-
Yujie Wu, Hanning Chen, Francesco Paesani, Feng Wang, and Gregory A. Voth
- Subjects
Models, Molecular ,Proton ,Surface Properties ,Binding energy ,Molecular Conformation ,Ab initio ,Thermodynamics ,Diffusion ,Materials Chemistry ,Cluster (physics) ,Molecule ,Computer Simulation ,Physics::Chemical Physics ,Physical and Theoretical Chemistry ,Chemistry ,Temperature ,Solvation ,Water ,Hydrogen Bonding ,Surfaces, Coatings and Films ,Models, Chemical ,Solubility ,Potential energy surface ,Solvents ,Valence bond theory ,Protons ,Atomic physics - Abstract
A new multistate empirical valence bond model (MS-EVB3) is developed for proton solvation and transport in aqueous solutions. The new model and its quantum version (qMS-EVB3) are based on the MS-EVB2 model [Day et al., J. Chem. Phys. 2002, 117, 5839] and recently developed flexible water models-the SPC/Fw model [Wu et al. J. Chem. Phys. 2006, 124, 24503] and the qSPC/Fw model [Paesani et al. J. Chem. Phys. 2006, 125, 184507]-for classical and quantum simulations, respectively. Using ab initio data as benchmarks, the binding energies and optimized geometries calculated with the new model for protonated water clusters, as well as the potential energy surface for proton shuttling between water molecules in a cluster environment, are improved in comparison to the MS-EVB2 model. For aqueous solutions, classical and quantum molecular dynamics simulations with the MS-EVB3 model yield a more accurate description of the solvation structure and diffusive dynamics of the excess proton. New insight is also provided into the proton solvation and hopping dynamics in water, as well as the "amphiphilic" nature of the hydrated proton that has been predicted to give rise to its enhanced concentration at aqueous interfaces and an effectively lower pH of the air-water interface [Petersen et al. J. Phys. Chem. B 2004, 108, 14804].
- Published
- 2007
Catalog
Discovery Service for Jio Institute Digital Library
For full access to our library's resources, please sign in.