Spectrum and infrared intensities of OH-stretching bands of water dimers

Prozument, Kirill; Choi, Myong Yong; Vilesov, Andrey F.

doi:10.1063/1.3276459

Cited by 123 publications

(186 citation statements)

References 73 publications

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“…Absorption intensity at 3735 cm −1 , obtained by subtraction of two spectra, was ascribed to the donor free OH stretch; this amounts to a shift of -21 cm −1 with respect to the monomer asymmetric stretch mode. The He droplet spectra of the water dimer 9 give a shift of -59.0 cm −1 for the donor bound OH stretch mode and two, not completely separated peaks with shifts of -25.3 and -26.3 cm −1 for the donor free OH stretch.…”

Section: Transitionmentioning

confidence: 99%

“…Some additional remarks can be made regarding the He nanodroplet spectra, 9 which show bands for all four OH stretch modes. Only for the acceptor asymmetric stretch mode a large splitting (7.8 cm −1 ) was measured, while for the other modes only a small splitting (1.0 cm −1 for the donor free OH stretch) or no splitting was observed.…”

Section: Transitionmentioning

confidence: 99%

“…These shifts are subjects of numerous measurements for hydrogen-bonded dimers and constitute a signature of the presence of hydrogen bonds. Although some of the IR shifts in the water dimer have been measured more than two decades ago, 5,20,21 new experimental data are still becoming available 9 and part of the existing data have been reassigned. The agreement between the previously calculated frequency shifts and the experimental data is still not as good as it is for the intermolecular modes.…”

Section: Introductionmentioning

confidence: 99%

“…1,4 The main source of experimental information on water dimer comes from spectral measurements. [5][6][7][8][9] The quest to reproduce the intermolecular rovibrational transitions began in the late 1990s when six-dimensional (6D) "exact" quantum nuclear dynamics calculations became possible. [10][11][12][13] In such calculations, the monomers are kept rigid, preferably at their average ground rovibrational state configuration.…”

Section: Introductionmentioning

confidence: 99%

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Spectra of water dimer from a new ab initio potential with flexible monomers

Leforestier

Szalewicz

Avoird

2012

The Journal of Chemical Physics

114

164

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Communication: Determination of the bond dissociation energy (D0) of the water dimer, (H2O)2, by velocity map imaging The Journal of Chemical Physics 134, 211101211101 (2011) We report the definition and testing of a new ab initio 12-dimensional potential for the water dimer with flexible monomers. Using our recent accurate CCpol-8s rigid water pair potential [W. Cencek, K. Szalewicz, C. Leforestier, R. van Harrevelt, and A. van der Avoird, Phys. Chem. Chem. Phys. 10, 4716 (2008)] as a reference for the undistorted monomers' geometries, a distortion correction has been added, which was taken from a former flexible-monomer ab initio potential. This correction allows us to retrieve the correct binding energy D e = 21.0 kJ mol −1 , and leads to an equilibrium geometry in close agreement with the one obtained from benchmark calculations. The kinetic energy operator describing the flexible-monomer water dimer has been expressed in terms of Radau coordinates for each monomer and a recent general cluster polyspherical formulation describing their relative motions. Within this formulation, an adiabatic scheme has been invoked in order to decouple fast (intramolecular) modes and slow (intermolecular) ones. Different levels of approximation were tested, which differ in the way in which the residual potential coupling between the intramolecular modes located on different monomers and the dependence of the monomer rotational constants on the dimer geometry are handled. Accurate calculations of the vibration-rotation-tunneling levels of (H 2 O) 2 and (D 2 O) 2 were performed, which show the best agreement with experiments achieved so far for any water potential. Intramolecular excitations of the two monomers were calculated within two limiting cases, to account for the lack of non-adiabatic coupling between intramolecular modes due to the intermolecular motion. In the first model, the excitation was assumed to stay either on the donor or the acceptor molecule, and to hop between the two moieties upon donor-acceptor interchange. In the second model, the excitation remains on the same molecule whatever is the dimer geometry. Marginal frequency differences, less than 2 cm −1 , were obtained for all modes, and the resulting infrared shifts are in good agreement with experiments.

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Section: Transitionmentioning

confidence: 99%

Section: Transitionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Spectra of water dimer from a new ab initio potential with flexible monomers

Leforestier

Szalewicz

Avoird

2012

The Journal of Chemical Physics

114

164

View full text Add to dashboard Cite

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“…The corresponding gas phase dimers show an intensity enhancement of about an order of magnitude 9,10,22 . Experiments by Kuyanov-Prozument et al on water dimers gives values of 44 and 144 km/mol for the monomer (asymmetric stretch) and dimer, respectively 23 .…”

Section: Computation Of the Infrared Intensitymentioning

confidence: 99%

Effect of hydrogen bonding on the infrared absorption intensity of OH stretch vibrations

2017

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We consider how the infrared intensity of an O-H stretch in a hydrogen bonded complex varies as the strength of the H-bond varies from weak to strong. We obtain trends for the fundamental and overtone transitions as a function of donor-acceptor distance R, which is a common measure of H-bond strength. Our calculations use a simple two-diabatic state model that permits symmetric and asymmetric bonds, i.e. where the proton affinity of the donor and acceptor are equal and unequal, respectively. The dipole moment function uses a Mecke form for the free OH dipole moment, associated with the diabatic states. The transition dipole moment is calculated using one-dimensional vibrational eigenstates associated with the H-atom transfer coordinate on the ground state adiabatic surface of our model. Over 20-fold intensity enhancements for the fundamental are found for strong H-bonds, where there are significant non-Condon effects. The isotope effect on the intensity yields a nonmonotonic H/D intensity ratio as a function of R, and is enhanced by the secondary geometric isotope effect. The first overtone intensity is found to vary non-monotonically with H-bond strength; strong enhancements are possible for strong H-bonds. Modifying the dipole moment through the Mecke parameters is found to have a stronger effect on the overtone than the fundamental. We compare our findings with those for specific molecular systems analysed through experiments and theory in earlier works. Our model results compare favourably for strong and medium strength symmetric H-bonds. However, for weak asymmetric bonds we find much smaller effects than in earlier work.

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Observation of the Low‐Frequency Spectrum of the Water Trimer as a Sensitive Test of the Water‐Trimer Potential and the Dipole‐Moment Surface

Schwan

Mani

et al. 2020

Angewandte Chemie

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Intermolecular interactions in bulk water are dominated by pairwise and non‐pairwise cooperative interactions. While accurate descriptions of the pairwise interactions are available and can be tested by precise low‐frequency spectra of the water dimer up to 550 cm−1, the same does not hold for the three‐body interactions. Here, we report the first comprehensive spectrum of the water trimer in the frequency region from 70 to 620 cm−1 using helium‐nanodroplet isolation and free‐electron lasers. By comparison to accompanying high‐level quantum calculations, the experimentally observed intermolecular bands can be assigned. The transition frequencies of the degenerate translation, the degenerate in‐plane and the non‐degenerate out‐of‐plane libration, as well as additional bands of the out‐of‐plane librational mode are reported for the first time. These provide a benchmark for state‐of‐the‐art water potentials and dipole‐moment surfaces, especially with respect to three‐body interactions.

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Spectrum and infrared intensities of OH-stretching bands of water dimers

Cited by 123 publications

References 73 publications

Spectra of water dimer from a new ab initio potential with flexible monomers

Spectra of water dimer from a new ab initio potential with flexible monomers

Effect of hydrogen bonding on the infrared absorption intensity of OH stretch vibrations

Observation of the Low‐Frequency Spectrum of the Water Trimer as a Sensitive Test of the Water‐Trimer Potential and the Dipole‐Moment Surface

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