Photoelectron spectrum of the water dimer

Tomoda, Shinji; Achiba, Yohji; Kimura, Katsumi

doi:10.1016/0009-2614(82)83586-0

Cited by 98 publications

(48 citation statements)

References 19 publications

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“…However, such interpretation is not consistent with the measured photoelectron spectrum of the water dimer: 80 the splitting of the b 1 peak amounts to 1.54 eV while the difference in the two appearance energies is only about 0.5 eV. The BHandHLYP method (with the splitting of 1.2 eV) reproduces well the experiment of Tomoda et al 80 while the LC-ωPBE method predicts somewhat lower splitting of about 0.9 eV.…”

Section: Evolution Of the Pe Spectra With The Cluster Sizementioning

confidence: 56%

“…To the best of our knowledge, there has not been any experimental photoelectron study involving all the valence peaks. We have compared our results with the measurements of Tomoda et al, 80 showing the splitting of the b 1 peak in the water dimer. The maximum of the first peak is energetically lower than the corresponding first peak of the water monomer, while the second is energetically higher (hydrogen bonding stabilization).…”

Section: A Assessment Of Electronic Structure Methods For Water Ionimentioning

confidence: 62%

“…Note that two appearance energies do not correspond to the onset of the two b 1 subpeaks. If we deconvolute the experimental photoelectron spectrum for a dimer, 80 we obtain the peak onsets 11.03 and 12.57 eV. energies is shown in Table VI.…”

Section: Evolution Of the Pe Spectra With The Cluster Sizementioning

confidence: 99%

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Simulations of light induced processes in water based on ab initio path integrals molecular dynamics. II. Photoionization

Svoboda

Ončák

Slavı́ček

2011

The Journal of Chemical Physics

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We have applied ab initio based reflection principle to simulate photoelectron spectra of small water clusters, ranging from monomer to octamer. The role of quantum and thermal effects on the structure of the water photoelectron spectra is discussed within the ab initio path integral molecular dynamics (PIMD) framework. We have used the PIMD method with up to 40 beads to sample the ground state quantum distribution at temperature T = 180 K. We have thoroughly tested the performance of various density functionals (B3LYP, BHandHLYP, M06HF, BNL, LC-ωPBE, and CAM-B3LYP) for the ionization process description. The benchmarking based on a comparison of simulated photoelectron spectra to experimental data and high level equation-of-motion ionization potential coupled clusters with singles and doubles calculations has singled out the BHandHLYP and LC-ωPBE functionals as the most reliable ones for simulations of light induced processes in water. The good performance of the density functional theory functionals to model the water photoelectron spectra also reflects their ability to reliably describe open shell excited states. The width of the photoelectron spectrum converges quickly with the cluster size as it is controlled by specific interactions of local character. The peak position is, on the other hand, defined by long-range non-specific solvent effects; it therefore only slowly converges to the corresponding bulk value. We are able to reproduce the experimental valence photoelectron spectrum of liquid water within the combined model of the water octamer embedded in a polarizable dielectric continuum. We demonstrate that including the long-range polarization and the state-specific treatment of the solvent response are needed for a reliable liquid water ionization description.

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Section: Evolution Of the Pe Spectra With The Cluster Sizementioning

confidence: 56%

Section: A Assessment Of Electronic Structure Methods For Water Ionimentioning

confidence: 62%

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Simulations of light induced processes in water based on ab initio path integrals molecular dynamics. II. Photoionization

Svoboda

Ončák

Slavı́ček

2011

The Journal of Chemical Physics

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“…Photoionization of a neutral water cluster (H 2 O) n is accompanied by a fast intracluster proton transfer with subsequent loss of an OH radical [28][29][30][31][32][33]: Accordingly we assign clusters with n molecules to VMIs recorded in coincidence with mass (n 18) 17 m = ⋅ − . For small clusters the subsequent slow loss of water molecules from the initially formed protonated cluster is dominated by monomer loss with total decay fractions < 0.3 [28,29,35].…”

Section: ( )mentioning

confidence: 99%

Size-Resolved Photoelectron Anisotropy of Gas Phase Water Clusters and Predictions for Liquid Water

et al. 2017

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We report the first measurement of size-resolved photoelectron angular distributions for the valence orbitals of water clusters with up to 20 molecules. A systematic decrease of the photoelectron anisotropy is found for clusters with up to 5-6 molecules, and most remarkably, convergence of the anisotropy for larger clusters. We suggest the latter to be the result of a local short-range scattering potential that is fully described by a unit of 5-6 molecules. The cluster data and a detailed electron scattering model are used to predict liquid water anisotropies. Reasonable agreement with experimental liquid jet data is found.A detailed understanding of elastic and inelastic scattering of electrons in liquid water is of fundamental importance for the modelling of radiation damage in biological systems, the description of the behaviour of the solvated electron in chemistry, and for the quantitative interpretation of photoelectron spectra of liquid water and aqueous solutions [1][2][3][4][5][6][7][8]. For slow electrons (electron kinetic energy eKE ≲ 50 eV), detailed experimental scattering parameters (differential scattering cross sections and energy losses) were so far only reported for amorphous ice [9]; with the exception of very slow electrons (eKE ≲ 6 eV), for which liquid water data were recently obtained from photoelectron velocity map imaging (VMI) of liquid water droplets [10]. Since there is little reason to expect substantial differences between amorphous ice and liquid water for electronic scattering processes (eKEs ≳ 6 eV) the amorphous ice and liquid droplet data [9,10] should now provide a reasonable data set for scattering simulations of liquid water. In addition, electron attenuation lengths (EALs) for eKEs ≳ 3 eV are available for liquid water from various microjet studies [11-13], which, however, do not allow quantitative predictions of the scattering contributions.The photoelectron angular distribution (PAD) is particularly sensitive to electron scattering and has thus recently received increasing attention in this context [7,10,[13][14][15][16][17][18]. Often, the information in the PAD is described by a single anisotropy parameter β (see Eq. ( 1)). For the liquid microjet, this is an approximation which we also follow in the present work. For ionization from the O1s orbital of liquid water, Thürmer et al. observed a more isotropic PAD; i. e. a smaller β-value; for liquid water compared with gas phase water over the eKE range from ~12 -450 eV [13]. For core-level ionization, this reduction is assumed to mainly arise from electron scattering within the liquid. For the ionization from the valence orbitals 1b 1 , 3a 1 , and 1b 2 , additional changes in the initial state due to orbital mixing also mediated by hydrogen-bonding are expected to contribute to the difference in β-values between gas and liquid phase. While monomer gas phase β-parameters have been reported for the three valence orbitals at photon energies 18 eV ≤ hν < 139 eV [15,16,[19][20][21], corresponding values for liquid water have t...

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“…The reaction of a water dimer cation following ionization is significantly different from that of a H 2 O monomer. A specific feature of this reaction is a fast proton transfer (PT) in the water dimer cation . Tomoda et al measured the HeI photoelectron spectrum of a gas‐phase water dimer produced in a supersonic nozzle beam below 13.5 eV .…”

Section: Introductionmentioning

confidence: 99%

Effects of zero point vibration on the reaction dynamics of water dimer cations following ionization

Tachikawa

2017

J Comput Chem

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Reactions of water dimer cation (H2O)2+ following ionization have been investigated by means of a direct ab initio molecular dynamics method. In particular, the effects of zero point vibration and zero point energy (ZPE) on the reaction mechanism were considered in this work. Trajectories were run on two electronic potential energy surfaces (PESs) of (H2O)2+: ground state ( A″-like state) and the first excited state ( A'-like state). All trajectories on the ground-state PES lead to the proton-transferred product: H O (Wd)-H O(Wa) → OH(Wd)-H O (Wa), where Wd and Wa refer to the proton donor and acceptor water molecules, respectively. Time of proton transfer (PT) varied widely from 15 to 40 fs (average time of PT = 30.9 fs). The trajectories on the excited-state PES gave two products: an intermediate complex with a face-to-face structure (H O-OH ) and a PT product. However, the proton was transferred to the opposite direction, and the reverse PT was found on the excited-state PES: H O(Wd)-H O (Wa) → H O (Wd)-OH(Wa). This difference occurred because the ionizing water molecule in the dimer switched between the ground and excited states. The reaction mechanism of (H2O)2+ and the effects of ZPE are discussed on the basis of the results. © 2017 Wiley Periodicals, Inc.

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Photoelectron spectrum of the water dimer

Cited by 98 publications

References 19 publications

Simulations of light induced processes in water based on ab initio path integrals molecular dynamics. II. Photoionization

Simulations of light induced processes in water based on ab initio path integrals molecular dynamics. II. Photoionization

Size-Resolved Photoelectron Anisotropy of Gas Phase Water Clusters and Predictions for Liquid Water

Effects of zero point vibration on the reaction dynamics of water dimer cations following ionization

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