Multireference configuration interaction calculation of the potential energy curves for OH bond breaking in the ground and lowest excited states of the water monomer and dimer

Sosa, Ramón M.; Gardiol, Patricia; Ventura, Oscar N.

doi:10.1016/0022-2860(93)80188-2

Cited by 13 publications

(10 citation statements)

References 39 publications

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“…Some aspects of excited electronic states and the photochemistry have been explored for the water dimer. [51][52][53][54][55] The potential-energy function for hydrogen transfer in the lowest excited singlet state of (H 2 O) 2 has been discussed by Sosa et al, 53 Kowal et al, 54 Sobolewski and Domcke 55 and Chipman. 49 It has been shown that a barrierless minimum-energy path for hydrogen transfer exists in the first excited singlet state of the water dimer.…”

Section: Photochemistry or Water Clustersmentioning

confidence: 99%

Computational studies of aqueous-phase photochemistry and the hydrated electron in finite-size clusters

Sobolewski

Domcke

2007

Phys. Chem. Chem. Phys.

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A survey of recent ab initio calculations on excited electronic states of water clusters and various chromophore-water clusters is given. Electron and proton transfer processes in these systems have been characterized by the determination of electronic wave functions, minimum-energy reaction paths and potential-energy profiles. It is pointed out that the transfer of a neutral hydrogen atom (leading to biradicals) rather than the transfer of a proton (leading to ion pairs) is the generic excited-state reaction mechanism in these systems. The hydrated hydronium radical, (H3O)(aq), plays a central role in this scenario. The electronic and vibrational spectra of H3O(H2O)(n) clusters and the decay mechanism of these metastable species have been investigated in some detail. The results suggest that (H3O)(aq) could be the carrier of the characteristic spectroscopic properties of the hydrated electron in liquid water.

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Section: Photochemistry or Water Clustersmentioning

confidence: 99%

Computational studies of aqueous-phase photochemistry and the hydrated electron in finite-size clusters

Sobolewski

Domcke

2007

Phys. Chem. Chem. Phys.

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“…The theoretical studies of the excited electronic states of the water dimer [13][14][15][16][17][18][19][20] have been mostly centered on their dependence on a reduced number of internal coordinates, with the remaining coordinates frozen to their equilibrium values. The theoretical studies of the excited electronic states of the water dimer [13][14][15][16][17][18][19][20] have been mostly centered on their dependence on a reduced number of internal coordinates, with the remaining coordinates frozen to their equilibrium values.…”

Section: Introductionmentioning

confidence: 99%

“…14 Recently, Chipman 17,18 has studied the dependence of the first excited electronic state on this coordinate of the water dimer in the icelike configuration, using the EOM-CCSD͑T͒ method with a aug-cc-pvtz atomic basis set. 14 Recently, Chipman 17,18 has studied the dependence of the first excited electronic state on this coordinate of the water dimer in the icelike configuration, using the EOM-CCSD͑T͒ method with a aug-cc-pvtz atomic basis set.…”

Section: Introductionmentioning

confidence: 99%

The photodissociation of the water dimer in the Ã band: A twelve-dimensional quasiclassical study

Avila

Kroes

Hemert

2008

The Journal of Chemical Physics

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The quasiclassical absorption spectrum of the water dimer in the A band was calculated taking into account motion in all degrees of freedom of the system. The ab initio excited state potentials employed were interpolated by the modified Shepard interpolation method using QMRCI energies and state-averaged MCSCF gradients and Hessians. The ground state vibrational wavefunction was variationally calculated using an adiabatic separation between the high and low frequency normal modes of the system. The calculated spectrum of water dimer shows a clear blueshift with respect to the monomer, but also a small red tail, in agreement with the prediction by Harvey et al. [J. Chem. Phys. 109, 8747 (1998)]. Previous three-dimensional model studies of the photodissociation of the water dimer by Valenzano et al. [J. Chem. Phys. 123, 034303 (2005)] did not show this red tail. A thorough analysis of the dependence of the spectrum on the modes coupled explicitly in the calculation of the spectrum shows that the red tail is due to coupling between the intramolecular stretch vibrations on different monomers.

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“…[10][11][12][13][14][15] Even fewer calculations explore excited state potential energy surfaces outside of the FranckCondon region, and these are generally limited to the dimer and other small water clusters. [16][17][18][19][20][21] Experimental measurements of the dynamics in the bulk liquid provide important benchmarks for comparison with theoretical and computational results.…”

Section: Introductionmentioning

confidence: 99%

Excited state dynamics of liquid water: Insight from the dissociation reaction following two-photon excitation

Elles

Shkrob

Crowell

et al. 2007

The Journal of Chemical Physics

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The authors use transient absorption spectroscopy to monitor the ionization and dissociation products following two-photon excitation of pure liquid water. The primary decay mechanism changes from dissociation at an excitation energy of 8.3 eV to ionization at 12.4 eV. The two channels occur with similar yield for an excitation energy of 9.3 eV. For the lowest excitation energy, the transient absorption at 267 nm probes the geminate recombination kinetics of the H and OH fragments, providing a window on the dissociation dynamics. Modeling the OH geminate recombination indicates that the dissociating H atoms have enough kinetic energy to escape the solvent cage and one or two additional solvent shells. The average initial separation of H and OH fragments is 0.7± 0.2 nm. Our observation suggests that the hydrogen bonding environment does not prevent direct dissociation of an O-H bond in the excited state. We discuss the implications of our measurement for the excited state dynamics of liquid water and explore the role of those dynamics in the ionization mechanism at low excitation energies.

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Multireference configuration interaction calculation of the potential energy curves for OH bond breaking in the ground and lowest excited states of the water monomer and dimer

Cited by 13 publications

References 39 publications

Computational studies of aqueous-phase photochemistry and the hydrated electron in finite-size clusters

Computational studies of aqueous-phase photochemistry and the hydrated electron in finite-size clusters

The photodissociation of the water dimer in the Ã band: A twelve-dimensional quasiclassical study

Excited state dynamics of liquid water: Insight from the dissociation reaction following two-photon excitation

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