Spectra of the D2O dimer in the O–D fundamental stretch region: Vibrational dependence of tunneling splittings and lifetimes

Barclay, A. J.; McKellar, A. R. W.; Moazzen‐Ahmadi, N.

doi:10.1063/1.5092503

Cited by 13 publications

(7 citation statements)

References 33 publications

(70 reference statements)

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“…where F is defined in Eq. 23 The calculation of ∆V in the PC basis is parallelized at two levels. First, as in paper I, the calculation of F is parallelized over Q β .…”

Section: Computing ∆V Matrixmentioning

confidence: 99%

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Computing excited OH stretch states of water dimer in 12D using contracted intermolecular and intramolecular basis functions

Wang

Carrington

2023

The Journal of Chemical Physics

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Due to the ubiquity and importance of water, water dimer has been intensively studied.Computing the (ro-)vibrational spectrum of water dimer is challenging. The potential has 8 wells separated by low barriers which makes harmonic approximations of limited utility. A variational approach is imperative, but difficult because there are 12 coupled vibrational coordinate. In this paper, we use a product contracted basis, whose functions are products of intramolecular and intermolecular functions computed using an iterative eigensolver. An intermediate matrix $\bs{F}$ facilitates calculating matrix elements. Using $\bs{F}$, it is possible to do calculations on a general potential without storing the potential on the full quadrature grid. We find that surprisingly many intermolecular functions are required. This is due to the importance of coupling between inter- and intra-molecular coordinates. The full $G_{16}$ symmetry of water dimer is exploited. We calculate, for the first time, monomer excited stretch states and compare $P(1)$ transition frequencies with their experimental counterparts. We also compare with experimental vibrational shifts and tunnelling splittings. Surprisingly, we find that the the largest tunnelling splitting, which does not involve interchange of the two monomers, is smaller in the asymmetric stretch excited state than in the ground state. Differences between levels we compute and those obtained with a [6+6] adiabatic approximation [Leforestier et al. J. Chem. Phys. {\bf{137}} 014305 (2012) ] are $\sim 0.6$ cm$^{-1}$ for states without monomer excitation, $\sim 4$ cm$^{-1}$ for monomer excited bend states, and as large as $\sim 10$ cm$^{-1}$ for monomer excited stretch states.

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“…where F is defined in Eq. 23 The calculation of ∆V in the PC basis is parallelized at two levels. First, as in paper I, the calculation of F is parallelized over Q β .…”

Section: Computing ∆V Matrixmentioning

confidence: 99%

“…For decades, the water dimer has been intensively studied by theorists [1][2][3][4][5][6][7][8][9][10][11][12] and experimentalists [13][14][15][16][17][18][19][20][21][22][23][24][25][26]. There are several review papers on water dimer [26][27][28][29][30][31].…”

Section: Introductionmentioning

confidence: 99%

Computing excited OH stretch states of water dimer in 12D using contracted intermolecular and intramolecular basis functions

Wang

Carrington

2023

The Journal of Chemical Physics

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“…Because cavity-confined water can have such a drastic effect on cavity-binding energetics (40), it is important to further study how the presence of bulk water destabilizes CB [5]-confined dimers. While this first study lacks the resolution to discern fine features such as rotational-tunneling transitions (13,41), it provides a valuable starting point for further measurement. Raman measurements from 200 to 700 cm −1 can access librational motions, key to hydrogen bond breaking/forming (42).…”

Section: Discussionmentioning

confidence: 99%

Tracking water dimers in ambient nanocapsules by vibrational spectroscopy

Hwang

Chikkaraddy

Grys

et al. 2022

Proc. Natl. Acad. Sci. U.S.A.

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Nanoconfined few-molecule water clusters are invaluable systems to study fundamental aspects of hydrogen bonding. Unfortunately, most experiments on water clusters must be performed at cryogenic temperatures. Probing water clusters in noncryogenic systems is however crucial to understand the behavior of confined water in atmospheric or biological settings, but such systems usually require either complex synthesis and/or introduce many confounding external bonds to the clusters. Here, we show that combining Raman spectroscopy with the molecular nanocapsule cucurbituril is a powerful technique to sequester and analyze water clusters in ambient conditions. We observe sharp peaks in vibrational spectra arising from a single rigid confined water dimer. The high resolution and rich information in these vibrational spectra allow us to track specific isotopic exchanges inside the water dimer, verified with density-functional theory and kinetic population modeling. We showcase the versatility of such molecular nanocapsules by tracking water cluster vibrations through systematic changes in confinement size, in temperatures up to 120° C, and in their chemical environment.

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“…This is consistent with the trend of vibrational frequencies extracted from the DFT calculations (Table S5). Moreover, the force constant of XÀ H (f X-H ) bond was derived by the Equation ( 1): [17] [18] Angewandte Chemie…”

Section: Methodsmentioning

confidence: 99%

Electrocatalytically Activating and Reducing N₂ Molecule by Tuning Activity of Local Hydrogen Radical

Yang

Shan

et al. 2023

Angew Chem Int Ed

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Decarbonizing N2 conversion is particularly challenging, but essential for sustainable development of industry and agriculture. Herein, we achieve electrocatalytic activation/reduction of N2 on X/Fe−N−C (X=Pd, Ir and Pt) dual‐atom catalysts under ambient condition. We provide solid experimental evidence that local hydrogen radical (H*) generated on the X site of the X/Fe−N−C catalysts can participate in the activation/reduction of N2 adsorbed on the Fe site. More importantly, we reveal that the reactivity of X/Fe−N−C catalysts for N2 activation/reduction can be well adjusted by the activity of H* generated on the X site, i.e., the interaction between the X−H bond. Specifically, X/Fe−N−C catalyst with the weakest X−H bonding exhibits the highest H* activity, which is beneficial to the subsequent cleavage of X−H bond for N2 hydrogenation. With the most active H*, the Pd/Fe dual‐atom site promotes the turnover frequency of N2 reduction by up to 10 times compared with the pristine Fe site.

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Spectra of the D2O dimer in the O–D fundamental stretch region: Vibrational dependence of tunneling splittings and lifetimes

Cited by 13 publications

References 33 publications

Computing excited OH stretch states of water dimer in 12D using contracted intermolecular and intramolecular basis functions

Computing excited OH stretch states of water dimer in 12D using contracted intermolecular and intramolecular basis functions

Tracking water dimers in ambient nanocapsules by vibrational spectroscopy

Electrocatalytically Activating and Reducing N₂ Molecule by Tuning Activity of Local Hydrogen Radical

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Spectra of the D2O dimer in the O–D fundamental stretch region: Vibrational dependence of tunneling splittings and lifetimes

Cited by 13 publications

References 33 publications

Computing excited OH stretch states of water dimer in 12D using contracted intermolecular and intramolecular basis functions

Computing excited OH stretch states of water dimer in 12D using contracted intermolecular and intramolecular basis functions

Tracking water dimers in ambient nanocapsules by vibrational spectroscopy

Electrocatalytically Activating and Reducing N2 Molecule by Tuning Activity of Local Hydrogen Radical

Contact Info

Product

Resources

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Electrocatalytically Activating and Reducing N₂ Molecule by Tuning Activity of Local Hydrogen Radical