Vibrational couplings and energy transfer pathways of water’s bending mode

Coupling between vibrational modes is essential for energy transfer and dissipation in condensed matter. For water, different O-H stretch modes are known to be very strongly coupled both within and between water molecules, leading to ultrafast dissipation and delocalization of vibrational energy. In contrast, the information on the vibrational coupling of the H-O-H bending mode of water is lacking, even though the bending mode is an essential intermediate for the energy relaxation pathway from the stretch mode to the heat bath. By combining static and femtosecond infrared, Raman, and hyper-Raman spectroscopies for isotopically diluted water with ab initio molecular dynamics simulations, we find the vibrational coupling of the bending mode differs significantly from the stretch mode: the intramode intermolecular coupling of the bending mode is very weak, in stark contrast to the stretch mode. Our results elucidate the vibrational energy transfer pathways of water. Specifically, the librational motion is essential for the vibrational energy relaxation and orientational dynamics of H-O-H bending mode.

Vibrational Couplings and Energy Transfer Pathways of Water’s Bending Mode

Coupling between vibrational modes is essential for energy transfer and dissipation in condensed matter. For water, different O-H stretch modes are known to be very strongly coupled both within and between water molecules, leading to ultrafast dissipation and delocalization of vibrational energy. In contrast, the information on the vibrational coupling of the H-O-H bending mode of water is lacking, even though the bending mode is an essential intermediate for the energy relaxation pathway from the stretch mode to the heat bath. By combining static and femtosecond infrared, Raman, and hyper-Raman spectroscopy with ab initio molecular dynamics simulations, we find the vibrational coupling of the bending mode differs significantly from the stretch mode: the intramode intermolecular coupling of the bending mode is very weak, in stark contrast to the stretch mode. Our results elucidate the vibrational energy transfer pathways of water. Specifically, the librational motion is essential for the vibrational energy relaxation and orientational dynamics of H-O-H bending mode.

Vibrational Couplings and Energy Transfer Pathways of Water’s Bending Mode

<p>Coupling between vibrational modes is essential for energy transfer and dissipation in condensed matter. For water, different O-H stretch modes are known to be very strongly coupled both within and between water molecules, leading to ultrafast dissipation and delocalization of vibrational energy. In contrast, the information on the vibrational coupling of the H-O-H bending mode of water is lacking, even though the bending mode is an essential intermediate for the energy relaxation pathway from the stretch mode to the heat bath. By combining static and femtosecond infrared, Raman, and hyper-Raman spectroscopy with<i> ab initio </i>molecular dynamics simulations, we find the vibrational coupling of the bending mode differs significantly from the stretch mode: the intramode intermolecular coupling of the bending mode is very weak, in stark contrast to the stretch mode. Our results elucidate the vibrational energy transfer pathways of water. Specifically, the librational motion is essential for the vibrational energy relaxation and orientational dynamics of H-O-H bending mode.</p>

Vibrational Couplings and Energy Transfer Pathways of Water’s Bending Mode

<p>Coupling between vibrational modes is essential for energy transfer and dissipation in condensed matter. For water, different O-H stretch modes are known to be very strongly coupled both within and between water molecules, leading to ultrafast dissipation and delocalization of vibrational energy. In contrast, the information on the vibrational coupling of the H-O-H bending mode of water is lacking, even though the bending mode is an essential intermediate for the energy relaxation pathway from the stretch mode to the heat bath. By combining static and femtosecond infrared, Raman, and hyper-Raman spectroscopy with<i> ab initio </i>molecular dynamics simulations, we find the vibrational coupling of the bending mode differs significantly from the stretch mode: the intramode intermolecular coupling of the bending mode is very weak, in stark contrast to the stretch mode. Our results elucidate the vibrational energy transfer pathways of water. Specifically, the librational motion is essential for the vibrational energy relaxation and orientational dynamics of H-O-H bending mode.</p>

Cavity molecular dynamics simulations of liquid water under vibrational ultrastrong coupling

We simulate vibrational strong coupling (VSC) and vibrational ultrastrong coupling (V-USC) for liquid water with classical molecular dynamics simulations. When the cavity modes are resonantly coupled to the O−H stretch mode of liquid water, the infrared spectrum shows asymmetric Rabi splitting. The lower polariton (LP) may be suppressed or enhanced relative to the upper polariton (UP) depending on the frequency of the cavity mode. Moreover, although the static properties and the translational diffusion of water are not changed under VSC or V-USC, we do find the modification of the orientational autocorrelation function of H2O molecules especially under V-USC, which could play a role in ground-state chemistry.

Structure and vibrational spectroscopy of lithium and potassium methanesulfonates

In this work, we have determined the structures of lithium methanesulfonate, Li(CH 3 SO 3 ), and potassium methanesulfonate, K(CH 3 SO 3 ), and analysed their vibrational spectra. The lithium salt crystallizes in the monoclinic space group C 2/ m with two formula units in the primitive cell. The potassium salt is more complex, crystallizing in I 4/ m with 12 formula units in the primitive cell. The lithium ion is fourfold coordinated in a distorted tetrahedron, while the potassium salt exhibits three types of coordination: six-, seven- and ninefold. Vibrational spectroscopy of the compounds (including the 6 Li and 7 Li isotopomers) confirms that the correlation previously found, that in the infrared spectra there is a clear distinction between coordinated and not coordinated forms of the methanesulfonate ion, is also valid here. The lithium salt shows a clear splitting of the asymmetric S–O stretch mode, indicating a bonding interaction, while there is no splitting in the spectrum of the potassium salt, consistent with a purely ionic material.

Thermal and Structure Analysis Based on Exfoliation of Clay in Thermosensitive Polymer by in-situ Polymerization

Poly(N-vinylcaprolactam) (PNVCL) offers superior characteristics as a thermoresponsive polymer for various potential applications. An attractive procedure, namely in-situ polymerization, was used to prepare NVCL/clay nanocomposite in different clay ratios. Organo-modified clay as C20 and B30 were employed in a range between 1–5% based on weight. Thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR) were used to study thermal decomposition and to assess bond conversion during polymerization of the nanocomposite. This research was conducted to study PNVCL characteristics with the addition of clay as a nanocomposite. The stretch mode of the carboxylic group (C=O) and (C=C) was present in the band range about ~1635 cm–1 for the C20, but it was ranging between 1640 to 1664 cm–1 for the B30 of the nanocomposite. It was observed that the decomposition was different for each type of organoclay and the temperature peaked at 30 to 800 °C, to measure the degradation points at 5, 10, and 50%. Comparison results for FTIR and TGA showed that the best nanocomposite was found in the C20 (3%) case.

Methanol C–O Bond Activation by Free Gold Clusters Probed via Infrared Photodissociation Spectroscopy

The activation of methanol (CD3OD and CD3OH) by small cationic gold clusters has been investigated via infrared multiphoton dissociation (IR-MPD) spectroscopy in the 615–1760 cm−1 frequency range. The C–O stretch mode around 925 cm−1 and a coupled CD3 deformation/C–O stretch mode around 1085 cm−1 are identified to be sensitive to the interaction between methanol and the gold clusters, whereas all other modes in the investigated spectral region remain unaffected. Based on the spectral shift of these modes, the largest C–O bond activation is observed for the mono-gold Au(CD3OD)+ cluster. This activation decreases with increasing the cluster size (number of gold atoms) and the number of adsorbed methanol molecules. Supporting density functional theory (DFT) calculations reveal that the C–O bond activation is caused by a methanol to gold charge donation, whereas the C–D and O–D bonds are not significantly activated by this process. The results are discussed with respect to previous experimental and theoretical investigations of neutral and cationic gold-methanol complexes focusing on the C–O stretch mode.