An ab initio study of the CrHe diatomic molecule: the effect of van der Waals distortion on a highly magnetic multi-electron system

Pototschnig, Johann Valentin; Ratschek, Martin; Hauser, Andreas; Ernst, Wolfgang

doi:10.1039/c4cp00559g

Cited by 3 publications

(18 citation statements)

References 64 publications

(81 reference statements)

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“…11−13 This section is divided into 6 subsections. We start with the discussion of the diatomic Cr–He PES 29 as basic requirements for the calculations. Second, we address the localization of the Cr on He N in different electronic states and compare our DFT results to qualitative predictions based on the Ancilotto parameter.…”

Section: Resultsmentioning

confidence: 99%

“…The Cr–He PES for the X 7 Σ + ground state (atomic a 7 S state) and the 1 5 Σ + lowest quintet state (atomic a 5 S) are taken from ref (29). In both cases, a Complete Active Space SCF (CASSCF) calculation was followed by a Davidson-corrected multireference calculation of second order (MRCI-Q).…”

Section: Resultsmentioning

confidence: 99%

“…The latter can be obtained from diatomic Cr–He potential energy curves, with Cr in the relevant electronic state. The wanted Cr–He potential curves for the X 7 Σ + ground state (a 7 S) and the lowest state in the quintet spin manifold, 1 5 Σ + (a 5 S), were taken from ref (29). Both are corrected for relativistic effects and finiteness of the basis set.…”

Section: Methodsmentioning

confidence: 99%

“…33 (The Π-states in the septet-multiplicity were unsuccessfully treated with coupled cluster (CC) methods. The open shell character of Cr prohibits a reliable treatment with CC methods as shown in ref (29). )…”

Section: Methodsmentioning

confidence: 99%

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Solvation and Spectral Line Shifts of Chromium Atoms in Helium Droplets Based on a Density Functional Theory Approach

et al. 2014

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The interaction of an electronically excited, single chromium (Cr) atom with superfluid helium nanodroplets of various size (10 to 2000 helium (He) atoms) is studied with helium density functional theory. Solvation energies and pseudo-diatomic potential energy surfaces are determined for Cr in its ground state as well as in the y7P, a5S, and y5P excited states. The necessary Cr–He pair potentials are calculated by standard methods of molecular orbital-based electronic structure theory. In its electronic ground state the Cr atom is found to be fully submerged in the droplet. A solvation shell structure is derived from fluctuations in the radial helium density. Electronic excitations of an embedded Cr atom are simulated by confronting the relaxed helium density (ρHe), obtained for Cr in the ground state, with interaction pair potentials of excited states. The resulting energy shifts for the transitions z7P ← a7S, y7P ← a7S, z5P ← a5S, and y5P ← a5S are compared to recent fluorescence and photoionization experiments.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Solvation and Spectral Line Shifts of Chromium Atoms in Helium Droplets Based on a Density Functional Theory Approach

et al. 2014

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“…The fact that Cr ions with attached helium atoms are detected in our experiments suggests that Cr–He n formation needs to be considered for the explanation of relaxation pathways and the description of the dynamics of Cr atoms inside helium droplets, calling for more sophisticated theoretical models. The Cr–He potential energy curves calculated in our group 43 can serve as a starting point for this task. Finally, it cannot be decided from our current data if ground state Cr atoms and Cr–He n complexes originate from excitation of single Cr atoms inside He N or a photoinduced dissociation of Cr dimers inside the droplet.…”

Section: Discussionmentioning

confidence: 99%

One- and Two-Color Resonant Photoionization Spectroscopy of Chromium-Doped Helium Nanodroplets

et al. 2014

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We investigate the photoinduced relaxation dynamics of Cr atoms embedded into superfluid helium nanodroplets. One- and two-color resonant two-photon ionization (1CR2PI and 2CR2PI, respectively) are applied to study the two strong ground state transitions z7P2,3,4° ← a7S3 and y7P2,3,4° ← a7S3. Upon photoexcitation, Cr* atoms are ejected from the droplet in various excited states, as well as paired with helium atoms as Cr*–Hen exciplexes. For the y7P2,3,4° intermediate state, comparison of the two methods reveals that energetically lower states than previously identified are also populated. With 1CR2PI we find that the population of ejected z5P3° states is reduced for increasing droplet size, indicating that population is transferred preferentially to lower states during longer interaction with the droplet. In the 2CR2PI spectra we find evidence for generation of bare Cr atoms in their septet ground state (a7S3) and metastable quintet state (a5S2), which we attribute to a photoinduced fast excitation–relaxation cycle mediated by the droplet. A fraction of Cr atoms in these ground and metastable states is attached to helium atoms, as indicated by blue wings next to bare atom spectral lines. These relaxation channels provide new insight into the interaction of excited transition metal atoms with helium nanodroplets.

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Photoinduced molecular dissociation and photoinduced recombination mediated by superfluid helium nanodroplets

Kautsch

Koch

Ernst

2015

Phys. Chem. Chem. Phys.

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We have investigated photoinduced chemical reaction dynamics of cold, isolated Cr2 molecules in helium nanodroplets (HeN), exploiting the quantum state specific spatial separation of solvated and surface locations on the droplet. The molecules are excited to achieve dissociation to a ground state (a(7)S3) and a metastable state (a(5)S2) atom. State specific spatial separation, in combination with efficient translational cooling to avoid ejection, causes the ground state atom to be solvated inside the droplet while the metastable atom migrates to the surface. A barrier between the two reactants formed by the HeN prevents recombination. We apply a resonance-enhanced multiphoton ionization scheme including the y(5)P°(1,2,3) <-- a(5)S(2) transition of the surface atom as well as a two-laser scheme including the y(7)P°(2,3,4) <-- a(7)S(3) transition of the solvated atom in order to verify the locations and separation of the dissociation products. Furthermore, ionization of the a(5)S2 surface atom triggers solvation followed by geminate recombination with the a(7)S3 atom, which is verified by the detection of Cr2(+) molecular ions. For small Cr clusters, our results indicate that they may be composed of chromium dimers that exhibit the same dissociation behavior.

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An ab initio study of the CrHe diatomic molecule: the effect of van der Waals distortion on a highly magnetic multi-electron system

Cited by 3 publications

References 64 publications

Solvation and Spectral Line Shifts of Chromium Atoms in Helium Droplets Based on a Density Functional Theory Approach

Solvation and Spectral Line Shifts of Chromium Atoms in Helium Droplets Based on a Density Functional Theory Approach

One- and Two-Color Resonant Photoionization Spectroscopy of Chromium-Doped Helium Nanodroplets

Photoinduced molecular dissociation and photoinduced recombination mediated by superfluid helium nanodroplets

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