Intermolecular Forces from the Spectroscopy of Van Der Waals Molecules

Hutson, Jeremy M.

doi:10.1146/annurev.pc.41.100190.001011

Cited by 290 publications

(124 citation statements)

References 2 publications

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“…[10][11][12][13][14][15][16][17] Spectroscopic studies on these complexes have focused on the molecular absorption corresponding to the strong atomic 2 P ← 2 S transition. The understanding of the bonding of such vdW complexes can be used to improve models of atom-surface interaction and study of chemical reaction dynamics, [18][19][20] while their decay by chemical exchange, pre-dissociation, and dissociation, can be controlled by external fields. Silver complexes with noble gas atoms can also be used for application to magnetometry, 21 and the pressure broadening and shift of the D 1 line of Ag in collisions with Ar and He were recently measured.…”

Section: Introductionmentioning

confidence: 99%

Potential energy curves for the interaction of Ag($\mathbf {5}{\bm s}$5s) and Ag($\mathbf {5}{\bm p}$5p) with noble gas atoms

Loreau

Sadeghpour

Dalgarno

2013

The Journal of Chemical Physics

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We investigate the interaction of ground and excited states of a silver atom with noble gases (NG), including helium. Born-Oppenheimer potential energy curves are calculated with quantum chemistry methods and spin-orbit effects in the excited states are included by assuming a spin-orbit splitting independent of the internuclear distance. We compare our results with experimentally available spectroscopic data, as well as with previous calculations. Because of strong spin-orbit interactions, excited Ag-NG potential energy curves cannot be fitted to Morse-like potentials. We find that the labeling of the observed vibrational levels has to be shifted by one unit.

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Section: Introductionmentioning

confidence: 99%

Potential energy curves for the interaction of Ag($\mathbf {5}{\bm s}$5s) and Ag($\mathbf {5}{\bm p}$5p) with noble gas atoms

Loreau

Sadeghpour

Dalgarno

2013

The Journal of Chemical Physics

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“…Using this detection technique and concepts, IR spectra of hundreds of van der Waals complexes (mostly below 4 monomer units) have been obtained during the last 20 years, contributing a great deal to our knowledge of intermolecular forces [7,9]. For larger sizes, many experiments investigate a single chromophore molecule complexed to a cluster of rare gas atoms, in order to keep the interactions as simple as possible.…”

Section: Introduction a Scope Of The Reviewmentioning

confidence: 99%

Helium nanodroplet isolation rovibrational spectroscopy: Methods and recent results

Callegari¹,

Lehmann²,

Schmied³

et al. 2001

The Journal of Chemical Physics

350

459

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In this article, recent developments in HElium NanoDroplet Isolation (HENDI) spectroscopy are reviewed, with an emphasis on the infrared region of the spectrum. We discuss how molecular beam spectroscopy and matrix isolation spectroscopy can be usefully combined into a method that provides a unique tool to tackle physical and chemical problems which had been outside our experimental possibilities. Next, in reviewing the experimental methodology, we present design criteria for droplet beam formation and its seeding with the chromophore(s) of interest, followed by a discussion of the merits and shortcomings of radiation sources currently used in this type of spectroscopy. In a second, more conceptual part of the review, we discuss several HENDI issues which are understood by the community to a varied level of depth and precision. In this context, we show first how a superfluid helium cluster adopts the symmetry of the molecule or complex seeded in it and discuss the nature of the potential well (and its isotropy) that acts on a solute inside a droplet, and of the energy levels that arise because of this confinement. Second, we treat the question of the homogeneous versus inhomogeneous broadening of the spectral profiles, moving after this to a discussion of the rotational dynamics of the molecules and of the surrounding superfluid medium. The change in rotational constants from their gas phase values, and their dependence on the angular velocity and vibrational quantum number are discussed. Finally, the spectral shifts generated by this very gentle matrix are analyzed and shown to be small because of a cancellation between the opposing action of the attractive and repulsive parts of the potential of interaction between molecules and their solvent. The review concludes with a discussion of three recent applications to (a) the synthesis of far-fromequilibrium molecular aggregates that could hardly be prepared in any other way, (b) the study of the influence of a simple and rather homogeneous solvent on large amplitude molecular motions, and (c) the study of mixed 3 He/ 4 He and other highly quantum clusters (e.g., H2 clusters) prepared inside helium droplets and interrogated by measuring the IR spectra of molecules embedded in them. In spite of the many open questions, we hope to convince the reader that HENDI has a great potential for the solution of several problems in modern chemistry and condensed matter physics, and that, even more interestingly, this unusual environment has the potential to generate new sets of issues which were not in our minds before its introduction.

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“…Much of our knowledge of intermolecular forces has come from the high-resolution spectroscopy of weakly bound closed shell complexes [1], and there is considerable promise that similar advances can be made for open shell complexes. Experimentally, the study of open shell reactive molecular complexes is more difficult than their closed shell counterparts due to the fact that their tendency to react must also be surpressed.…”

Section: Introductionmentioning

confidence: 99%

A high-resolution infrared spectroscopic investigation of the halogen atom–HCN entrance channel complexes solvated in superfluid helium droplets

Merritt

Küpper

Miller

2007

Phys. Chem. Chem. Phys.

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Rotationally resolved infrared spectra are reported for the X-HCN (X = Cl, Br, I) binary complexes solvated in helium nanodroplets. These results are directly compared with that obtained previously for the corresponding X-HF complexes [J. M. Merritt, J. Küpper, and R. E. Miller, PCCP, 7, 67 (2005)]. For bromine and iodine atoms complexed with HCN, two linear structures are observed and assigned to the 2 Σ 1/2 and 2 Π 3/2 ground electronic states of the nitrogen and hydrogen bound geometries, respectively. Experiments for HCN + chlorine atoms give rise to only a single band which is attributed to the nitrogen bound isomer. That the hydrogen bound isomer is not stabilized is rationalized in terms of a lowering of the isomerization barrier by spin-orbit coupling. Theoretical calculations with and without spin-orbit coupling have also been performed and are compared with our experimental results. The possibility of stabilizing high-energy structures containing multiple radicals is discussed, motivated by preliminary spectroscopic evidence for the di-radical Br-HCCCN-Br complex. Spectra for the corresponding molecular halogen HCN-X2 complexes are also presented.

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Intermolecular Forces from the Spectroscopy of Van Der Waals Molecules

Cited by 290 publications

References 2 publications

Potential energy curves for the interaction of Ag($\mathbf {5}{\bm s}$5s) and Ag($\mathbf {5}{\bm p}$5p) with noble gas atoms

Potential energy curves for the interaction of Ag($\mathbf {5}{\bm s}$5s) and Ag($\mathbf {5}{\bm p}$5p) with noble gas atoms

Helium nanodroplet isolation rovibrational spectroscopy: Methods and recent results

A high-resolution infrared spectroscopic investigation of the halogen atom–HCN entrance channel complexes solvated in superfluid helium droplets

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