<i>Ab initio</i> Modeling of the Vibrational Sum-Frequency Generation Spectrum of Interfacial Water

Liang, Chungwen; Jeon, Jonggu; Cho, Minhaeng

doi:10.1021/acs.jpclett.9b00291

Cited by 37 publications

(42 citation statements)

References 47 publications

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“…For example, the spectra calculated at the PBE-D3m(BJ), BLYP-D2, and PBE-rVV10 functionals show a small, but non-negligible positive band below 2100 cm –1 . This is in line with a claim of ref (24). However, Figure 1 clearly illustrates that all the XC functionals showing a positive 2100 cm –1 band do not reproduce the water properties accurately, implying that the presence of the positive 2100 cm –1 band may arise from the poor description of the interfacial water.…”

supporting

confidence: 93%

Accessing the Accuracy of Density Functional Theory through Structure and Dynamics of the Water–Air Interface

Ohto

Dodia

et al. 2019

J. Phys. Chem. Lett.

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Density functional theory-based molecular dynamics simulations are increasingly being used for simulating aqueous interfaces. Nonetheless, the choice of the appropriate density functional, critically affecting the outcome of the simulation, has remained arbitrary. Here, we assess the performance of various exchange–correlation (XC) functionals, based on the metrics relevant to sum-frequency generation spectroscopy. The structure and dynamics of water at the water–air interface are governed by heterogeneous intermolecular interactions, thereby providing a critical benchmark for XC functionals. We find that the XC functionals constrained by exact functional conditions (revPBE and revPBE0) with the dispersion correction show excellent performance. The poor performance of the empirically optimized density functional (M06-L) indicates the importance of satisfying the exact functional condition. Understanding the performance of different XC functionals can aid in resolving the controversial interpretation of the interfacial water structure and direct the design of novel, improved XC functionals better suited to describing the heterogeneous interactions in condensed phases.

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supporting

confidence: 93%

Accessing the Accuracy of Density Functional Theory through Structure and Dynamics of the Water–Air Interface

Ohto

Dodia

et al. 2019

J. Phys. Chem. Lett.

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“…68 However, the response of the SFG signal is based on the second-order nonlinear optical process, and the strength of the SFG signal depends on the number of molecules present at the interface and their net average orientation. 72 The adsorption of protein molecules at the interface can disrupt the interfacial water molecules and therefore reduce the surface free energy. As a consequence, the value of the surface tension would decrease and may continue as long as the adsorption of the protein molecules is dominated at the surface.…”

Section: Resultsmentioning

confidence: 99%

Probing the Bovine Hemoglobin Adsorption Process and its Influence on Interfacial Water Structure at the Air–Water Interface

Chaudhary

Kaur

et al. 2021

Appl Spectrosc

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* These authors contributed equally to this work. The molecular-level insight of protein adsorption and its kinetics at interfaces is crucial because of its multifold role in diverse fundamental biological processes and applications. In the present study, the sum frequency generation (SFG) vibrational spectroscopy has been employed to demonstrate the adsorption process of bovine hemoglobin (BHb) protein molecules at the air–water interface at interfacial isoelectric point of the protein. It has been observed that surface coverage of BHb molecules significantly influences the arrangement of the protein molecules at the interface. The time-dependent SFG studies at two different frequencies in the fingerprint region elucidate the kinetics of protein denaturation process and its influence on the hydrogen-bonding network of interfacial water molecules at the air–water interface. The initial growth kinetics suggests the synchronized behavior of protein adsorption process with the structural changes in the interfacial water molecules. Interestingly, both the events carry similar characteristic time constants. However, the conformational changes in the protein structure due to the denaturation process stay for a long time, whereas the changes in water structure reconcile quickly. It is revealed that the protein denaturation process is followed by the advent of strongly hydrogen-bonded water molecules at the interface. In addition, we have also carried out the surface tension kinetics measurements to complement the findings of our SFG spectroscopic results.

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“…For that purpose, the fluctuations in the dipole moment are obtained using the Wannier centers, whereas the components of the polarizability tensor are approximated using the second moment of the Wannier centers. However, it is noteworthy that several other computational studies have obtained the vSFG spectrum using empirical maps [ 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 ], velocity correlations [ 41 , 42 , 43 , 44 ], as well as directly from AIMD simulations [ 45 , 46 , 47 , 48 ].…”

Section: Introductionmentioning

confidence: 99%

“On-The-Fly” Calculation of the Vibrational Sum-Frequency Generation Spectrum at the Air-Water Interface

Ojha

Kühne

2020

Molecules

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In the present work, we provide an electronic structure based method for the “on-the-fly” determination of vibrational sum frequency generation (v-SFG) spectra. The predictive power of this scheme is demonstrated at the air-water interface. While the instantaneous fluctuations in dipole moment are obtained using the maximally localized Wannier functions, the fluctuations in polarizability are approximated to be proportional to the second moment of Wannier functions. The spectrum henceforth obtained captures the signatures of hydrogen bond stretching, bending, as well as low-frequency librational modes.

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Ab initio Modeling of the Vibrational Sum-Frequency Generation Spectrum of Interfacial Water

Cited by 37 publications

References 47 publications

Accessing the Accuracy of Density Functional Theory through Structure and Dynamics of the Water–Air Interface

Accessing the Accuracy of Density Functional Theory through Structure and Dynamics of the Water–Air Interface

Probing the Bovine Hemoglobin Adsorption Process and its Influence on Interfacial Water Structure at the Air–Water Interface

“On-The-Fly” Calculation of the Vibrational Sum-Frequency Generation Spectrum at the Air-Water Interface

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