Kinematically complete final state investigations of molecular photodissociation: two- and three-body decay of laser-prepared H33 s 2 A1'

Galster, U.; Kamiński, P.; Beckert, M.; Helm, H.; Müller, Ulrich

doi:10.1007/s100530170005

Cited by 21 publications

(22 citation statements)

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“…[39] for an overview). Furthermore, more recent photodissociation data [40] indicate a somewhat lower value of 4.337 eV for the H + 3 binding energy [41], closer to the theoretical results. Based on the accuracy that calculations of the H + 3 potential surface have reached and the agreement among the published values, we use the theoretical value as our reference.…”

Section: A H + 3 Rotational Energy By Dr Fragment Imagingsupporting

confidence: 81%

High-resolution storage-ring measurements of the dissociative recombination ofH3+using a supersonic expansion ion source

et al. 2010

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We have performed measurements of the dissociative electron recombination (DR) of H + 3 at the ion storage ring TSR utilizing a supersonic expansion ion source. The ion source has been characterized by continuous wave cavity ring-down spectroscopy. We present high-resolution DR rate coefficients for different nuclear spin modifications of H + 3 combined with precise fragment imaging studies of the internal excitation of the H + 3 ions inside the storage ring. The measurements resolve changes in the energy dependence between the ortho-H + 3 and para-H + 3 rate coefficients at low center-of-mass collision energies. Analysis of the imaging data indicates that the stored H + 3 ions may have higher rotational temperatures than previously assumed, most likely due to collisional heating during the extraction of the ions from the ion source. Simulations of the ion extraction shed light on possible origins of the heating process and how to avoid it in future experiments.

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Section: A H + 3 Rotational Energy By Dr Fragment Imagingsupporting

confidence: 81%

High-resolution storage-ring measurements of the dissociative recombination ofH3+using a supersonic expansion ion source

et al. 2010

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“…This fact has motivated a multitude of laboratory studies on this species, such as studies of dissociative recombination of H 3 + conducted in storage rings (e.g., [1][2][3][4][5]), dissociative collisions (e.g., [6][7][8]), and weakfield laser spectroscopy [9,10]. For similar reasons, exploring the nonlinear behavior of H 3 + (or D 3 + ) in ultrashort intense laser fields is desirable as it can lead to a better understanding of the laser-driven dynamics of polyatomic molecules-in a similar way that H 2 + has been a benchmark system for studies of diatomic molecules [11,12].…”

Section: Introductionmentioning

confidence: 99%

Dynamics of D3+slow dissociation induced by intense ultrashort laser pulses

et al. 2012

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The dissociation of D 3 + in intense ultrashort laser pulses is investigated using an improved coincidence three-dimensional momentum imaging method that allows clear separation of all fragmentation channels and the determination of the kinetic energy release down to zero. Our results, using 10-fs, 790-nm pulses, suggest that a large peak at low kinetic energy release is associated with the D + + D 2 dissociation channel of D 3 + . The most likely dissociation pathways leading to two-body breakup of D 3 + are identified with additional measurements using 25-fs, 790-nm and 40-fs, 395-nm pulses. We also show that the slow D + + D 2 dissociation dynamics can be manipulated by the pulse duration.

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“…Although the ground state of triatomic molecular hydrogen is not a chemically stable compound, its threebody photodissociation has been well studied employing stable H + 3 ions in conjunction with electron pick-up methodolgies [117][118][119][120][121]. Accordingly, the present predictions, reporting atomic-state entanglements having potentially measureable consequences in a simple wellstudied triatomic molecule, would seem to provide an opportunity for corresponding experimental studies.…”

Section: Atomic State Promotion Probabilities In Diatomic Hydrogenmentioning

confidence: 85%

“…Additional calculation of atomic promotion and interaction energies in low-lying triatomic hydrogen states not reported here, which include three-body dissociation pathways relevant to Dalitz plot geometries conveniently accessible to experimental observations [117][118][119][120][121], have been reported separately elsewhere [91]. These calculations include in particular symmetric C 3v triatomic dissociations particularly well-suited for experimental observation in view of the corresponding equilibrium stucture of the precursor H + 3 ion.…”

Section: Atomic State Promotion Probabilities In Diatomic Hydrogenmentioning

confidence: 95%

Quantum-mechanical definition of atoms and their mutual interactions in Born-Oppenheimer molecules

2018

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The apparent absence of meaningful assignments of electrons and indistinguishable nuclei to particular atoms in a chemical aggregate would seem to preclude quantum-mechanical definition of atomic Hamiltonian operators within molecules and matter. The electronic energies of individual constituent atoms, as well as the interactions between them, are accordingly widely perceived as objectively undefined in molecular quantum theory, requiring additional auxiliary conditions to achieve quantitative specificity, giving rise to a plethora of individual preferences. Here we address the issue of assignments of electrons to atoms within molecules at the Born-Oppenheimer classical "fixednuclei" level of theory, and provide thereby quantum-mechanical definitions of atomic operators and of the interactions between them. In the spirit of early work of Longuet-Higgins, a "van-der-Waals" subgroup of the full molecular electronic symmetric group is shown to facilitate assignments of electrons to particular atomic nuclei in a molecule. The orthonormal (Eisenschitz-London) outerproducts of atomic eigenstates that provide separable Hilbert space representations of this symmetric subgroup furthermore support totally antisymmetric solutions of the molecular Schrödinger equation. Self-adjoint atomic and atomic-interaction operators within a molecule defined in this way are seen to have universal Hermitian matrix representatives and physically significant expectation values in totally antisymmetric molecular eigenstates. Adiabatic Born-Oppenheimer molecular energies emerge naturally from the development in the form of sums of the energies of individual atomic constituents, and of their atomic pairwise interactions, in the absence of additional auxiliary conditions. A detailed and nuanced quantitative description of electronic structure and bonding is provided thereby which includes the interplay between atomic promotion and intereaction energies, common representations of atomic-state hybridization and inter-atomic charge apportionment, potentially measurable multi-atom entanglements upon coherent dissociations of molecules, and other attributes of the development revealed by selected illustrative calculations. These include applications to the ground and electronically excited states of diatomic and triatomic hydrogen molecules, which exhibit significant accommodation among the atomic promotion and interaction energies, as well as entanglements among atomic states, over the entire range of molecular geometries transversed in the course of two-and three-atom dissociations.

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Kinematically complete final state investigations of molecular photodissociation: two- and three-body decay of laser-prepared H33 s 2 A1'

Cited by 21 publications

References 1 publication

High-resolution storage-ring measurements of the dissociative recombination ofH3+using a supersonic expansion ion source

High-resolution storage-ring measurements of the dissociative recombination ofH3+using a supersonic expansion ion source

Dynamics of D3+slow dissociation induced by intense ultrashort laser pulses

Quantum-mechanical definition of atoms and their mutual interactions in Born-Oppenheimer molecules

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