Van Der Waals Molecules

Levy, Donald H.

doi:10.1002/9780470142677.ch6

Cited by 195 publications

(6 citation statements)

References 66 publications

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“…This study expands on our previous efforts, which have been focused on the characterization of multidimensional potential energy surfaces (PESs), and higher-order conformers of weakly bound rare gas–dihalogen clusters. − Thus, combinations of rare-gas atoms with halogen molecules have been studied by both experiment and theory. − In these studies on rare gas-solvated molecules, questions relating to intermolecular interactions, energy transfer mechanisms, and solvation structures have been addressed. ,,− More recently, such complexes have also received further attention due to the development of techniques for synthesizing and characterizing doped helium nanodroplets. , Apart from such studies, recent experimental observations from laser-induced-fluorescence (LIF) and two-color action spectroscopy techniques have stabilized multiple conformers of higher size rare-gas dihalogen clusters …”

Section: Introductionmentioning

confidence: 90%

Quantum Mechanical Characterization of the He₄ICl Weakly Bound Complex

Valdés

Prosmiti

2013

J. Phys. Chem. A

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Vibrational calculations are performed for the 12-dimensional He4ICl van der Waals complex using the multiconfiguration time-dependent Hartree (MCTDH) method. The potential energy surface of the cluster is represented as a sum of the triatomic He–ICl ab initio parametrized terms plus the He–He interactions. The topology of the potential presents higher anisotropy compared to the one with a homonuclear dopant, and this is clearly reflected in the structure and energetics of the low-lying conformers of the system. In order to take advantage of the MCTDH method, natural potential fits are employed for the potential energy operator, and also, a mode combination scheme is introduced in order to speed up the computations. Zero-point energy, binding energies, and vibrationally averaged structures of different isomers of the He4ICl cluster are obtained. The present results predict that the (3,1,0) structure, involving three He atoms in the near T-shaped and one He atom in the linear configurations, to be the most stable one in accord with recent experimental findings. Comparisons with previous theoretical and experimental data are presented, and the stability of the high-order conformers is discussed in connection with the multiple minima (global and local) of the underlying potential surface.

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Section: Introductionmentioning

confidence: 90%

Quantum Mechanical Characterization of the He₄ICl Weakly Bound Complex

Valdés

Prosmiti

2013

J. Phys. Chem. A

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“…The electronic configuration of the ground 2 3 ) linear configuration. Jacobi coordinates (r, R, θ ) are employed for the description of the PES of the HeI 2 complex, where R is the intermolecular distance of the He atom from the center of mass of I 2 , r is the bond length of iodine, and θ is the angle defined by the R and r vectors.…”

Section: A Ab Initio Electronic Structure Calculationsmentioning

confidence: 99%

Theoretical investigation of the He–I2(E3Πg) ion-pair state: Ab initio intermolecular potential and vibrational levels

Καλέμος

Valdés

Prosmiti

2012

The Journal of Chemical Physics

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We present a theoretical study on the potential energy surface and vibrational bound states of the E electronic excited state of the HeI 2 van der Waals system. The interaction energies are computed using accurate ab initio methods and large basis sets. Relativistic small-core effective core potentials in conjunction with a quintuple-zeta quality basis set are employed for the heavy iodine atoms in multireference configuration interaction calculations for the 3 A and 3 A states. For the representation of the potential energy surface we used a general interpolation technique for constructing potential surfaces from ab initio data based on the reproducing kernel Hilbert space method. The surface presents global and local minima for T-shaped configurations with well-depths of 33.2 and 4.6 cm −1 , respectively. Vibrational energies and states are computed through variational quantum mechanical calculations. We found that the binding energy of the HeI 2 (E) T-shaped isomer is 16.85 cm −1 , in excellent agreement with recent experimental measurements. In lieu of more experimental data we also report our predictions on higher vibrational levels and we analyze the influence of the underlying surface on them. This is the first attempt to represent the potential surface of such a highly excited electronic state of a van der Waals complex, and it demonstrates the capability of the ab initio technology to provide accurate results for carrying out reliable studies to model experimental data.

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“…Rare gas-dihalogen (Rg···XY) van der Waals complexes have been extensively studied over the last 45 years as a means to investigate unimolecular reaction dynamics, energy transfer mechanisms, and intermolecular forces. − In part because of their strong absorption throughout the visible and ultraviolet regions and the relative simplicity of these three-atom systems, the Rg···XY complexes are well suited for both experimental and theoretical efforts, and accurate depictions of the chemical physics continue to be established. The vibrational predissociation (VP) dynamics of Rg···XY complexes, in particular, have been utilized to investigate vibrational to rotational energy transfer dynamics.…”

Section: Introductionmentioning

confidence: 99%

Probing the Dependence of Long-Range, Four-Atom Interactions on Intermolecular Orientation. 4. The Dissociation Dynamics of H₂/D₂···ICl(B,v′=3) and the Observation of Efficient Vibrational–Rotational Energy Transfer

Darr

Loomis

2022

J. Phys. Chem. A

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The vibrational predissociation dynamics of H2/D2···I35Cl(B,v′=3) complexes containing both para- and ortho-hydrogen prepared in different intermolecular vibrational levels were investigated. The Δv = −1 I35Cl(B,v = 2,j) rotational product-state distributions measured for excitation to the lowest-energy T-shaped levels of these complexes are mostly bimodal. The rotational distributions measured for excitation of the H2···I35Cl(B,v′=3) complexes are colder than those of the D2···I35Cl(B,v′=3) complexes, and there are only slight differences between those measured for the para- and ortho-hydrogen containing complexes. Excitation of the delocalized bending levels results in slightly colder rotational product-state distributions. The distributions suggest the dynamics result from more than impulsive dissociation off of the inner repulsive wall of the lower-energy H2/D2 + I35Cl(B,v = 2) potential surfaces of the products. The depths of these potentials and the energies available to these products also contribute to the dynamics. The formation of the Δv = −2, I35Cl(B,v = 1) product channel was only identified for excitation of levels within the ortho(j = 0)-D2 + I35Cl(B,v′=3) potential. The formation of this channel occurs via I35Cl(B,v′=3) vibrational to D2 rotational energy transfer forming the ortho(j = 2)-D2 + I35Cl(B,v = 1,j) products.

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Van Der Waals Molecules

Cited by 195 publications

References 66 publications

Quantum Mechanical Characterization of the He₄ICl Weakly Bound Complex

Quantum Mechanical Characterization of the He₄ICl Weakly Bound Complex

Theoretical investigation of the He–I2(E3Πg) ion-pair state: Ab initio intermolecular potential and vibrational levels

Probing the Dependence of Long-Range, Four-Atom Interactions on Intermolecular Orientation. 4. The Dissociation Dynamics of H₂/D₂···ICl(B,v′=3) and the Observation of Efficient Vibrational–Rotational Energy Transfer

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Van Der Waals Molecules

Cited by 195 publications

References 66 publications

Quantum Mechanical Characterization of the He4ICl Weakly Bound Complex

Quantum Mechanical Characterization of the He4ICl Weakly Bound Complex

Theoretical investigation of the He–I2(E3Πg) ion-pair state: Ab initio intermolecular potential and vibrational levels

Probing the Dependence of Long-Range, Four-Atom Interactions on Intermolecular Orientation. 4. The Dissociation Dynamics of H2/D2···ICl(B,v′=3) and the Observation of Efficient Vibrational–Rotational Energy Transfer

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Quantum Mechanical Characterization of the He₄ICl Weakly Bound Complex

Quantum Mechanical Characterization of the He₄ICl Weakly Bound Complex

Probing the Dependence of Long-Range, Four-Atom Interactions on Intermolecular Orientation. 4. The Dissociation Dynamics of H₂/D₂···ICl(B,v′=3) and the Observation of Efficient Vibrational–Rotational Energy Transfer