Vibrational spectra of dissociatively adsorbed D2O on Al-terminated α-Al2O3(0001) surfaces from ab initio molecular dynamics

Abstract

Toward ab initio molecular dynamics modeling for sum-frequency generation spectra; an efficient algorithm based on surface-specific velocity-velocity correlation function

Effects of stearyl alcohol monolayer on the structure, dynamics and vibrational sum frequency generation spectroscopy of interfacial water

“…This method can be further sub-divided into the use of empirical flexible force-field based simulations 22,48,[54][55][56][57][58][59] or ab initio molecular dynamics simulations. [60][61][62][63][64][65][66] In the second or the time-independent approach, the transition frequencies and the dipole and polarizability components of eqn (2) and ( 5) are obtained through spectral mapping techniques which are derived through a large number of static quantum chemical calculations of smaller cluster systems containing the vibrational chromophore of interest. [67][68][69][70] In this technique, the simulations are generally carried out using simpler rigid-body force-fields since the frequencies and other parameters are obtained from spectral mapping procedures and not directly from intramolecular vibrational fluctuations along the simulation trajectories.…”

Molecular Structure and Modeling of Water–Air and Ice–Air Interfaces Monitored by Sum-Frequency Generation

“…A number of research groups, including Sulpizi/Gaigeot/Sprik, ,− Galli, Luber,Cho, Klein/Bourget, , Saalfrank, , Chandra, and Car/Selloni groups as well as Nagata/Bonn group ,− have used AIMD simulation for computing the SFG spectra. Because the forces acting on the atoms are calculated within the electronic structure theory in the AIMD simulation, one does not need force field models.…”

Vibrational energy relaxation of interfacial OH on a water-covered α-Al2O3(0001) surface: a non-equilibrium ab initio molecular dynamics study

“…In this case, dipole-dipole auto-or dipole-polarizability cross-correlation functions need to be determined, which can also be done with the help of velocityvelocity autocorrelation functions. 22,23,45 Work along these lines is in progress in our laboratory.…”

“…In own recent work, in a combined experimental/theoretical effort, the so-called Al-I terminated a-Al 2 O 3 (0001) surface [18][19][20][21][22] as the most stable alumina surface in vacuum, [19][20][21][22] further a hydroxylated a-Al 2 O 3 (0001), 21,23 as well as O-terminated a-Al 2 O 3 (1% 102) 24 and O-terminated a-Al 2 O 3 (11% 20) 25 surfaces, all in contact with small amounts of water were studied with steady-state VSF spectroscopy, mostly to characterize the vibrations of interfacial O-H (or O-D) bonds. From the theory side, periodic Density Functional Theory (DFT) was used, either stationary and together with Normal Mode Analysis (NMA), 20,21,24,25 or in the form of ab initio molecular dynamics (AIMD) in combination with Time-dependent Correlation Function (TCF) methods, 22,23 to characterize adsorbate vibrations. The AIMD/TCF approach is computationally costly but also very powerful, as it accounts for Vibrational Density Of States (VDOS) curves and even for spectra, IR and VSF, 22,23 beyond the harmonic approximation and it explicitly includes the effects of temperature, which allows for direct comparison between simulations and experiments.…”

“…From the theory side, periodic Density Functional Theory (DFT) was used, either stationary and together with Normal Mode Analysis (NMA), 20,21,24,25 or in the form of ab initio molecular dynamics (AIMD) in combination with Time-dependent Correlation Function (TCF) methods, 22,23 to characterize adsorbate vibrations. The AIMD/TCF approach is computationally costly but also very powerful, as it accounts for Vibrational Density Of States (VDOS) curves and even for spectra, IR and VSF, 22,23 beyond the harmonic approximation and it explicitly includes the effects of temperature, which allows for direct comparison between simulations and experiments.…”