Quantum chemistry of confined systems: structure and vibronic spectra of a confined hydrogen molecule

Bielińska-Wąż, Dorota; Diercksen, Geerd H. F.; Kłobukowski, Mariusz

doi:10.1016/s0009-2614(01)01226-x

Cited by 66 publications

(41 citation statements)

References 11 publications

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“…However, they can be presented in the broad context of experiences and knowledge emerging from computational and experimental studies concerning the effects of spatial restriction or high pressure on the individual molecules View Article Online and molecular materials. 8,15,16,[53][54][55][56][57] Our results presented in the Table 2 support the findings reported by other authors, since for all the investigated molecules the same trends are observed. Indeed, it has been shown that high pressure induces significant changes of position and intensity of vibrational bands in the IR and Raman spectra of molecules in various molecular materials.…”

supporting

confidence: 92%

On the particular importance of vibrational contributions to the static electrical properties of model linear molecules under spatial confinement

Zaleśny

Góra

Luis

et al. 2015

Phys. Chem. Chem. Phys.

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The influence of the spatial confinement on the electronic and vibrational contributions to longitudinal electric-dipole properties of model linear molecules including HCN, HCCH and CO2 is discussed. The effect of confinement is represented by two-dimensional harmonic oscillator potential of cylindrical symmetry, which mimics the key features of various types of trapping environments like, for instance, nanotubes or quantum well wires. Our results indicate that in general both (electronic and vibrational) contributions to (hyper)polarizabilities diminish upon spatial confinement. However, since the electronic term is particularly affected, the relative importance of vibrational contributions is larger for confined species. This effect increases also with the degree of anharmonicity of vibrational motion.

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supporting

confidence: 92%

On the particular importance of vibrational contributions to the static electrical properties of model linear molecules under spatial confinement

Zaleśny

Góra

Luis

et al. 2015

Phys. Chem. Chem. Phys.

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“…The influence of such an environment to the embedded system depends on the distance between this system and atoms which form the repulsive wall. 16 Most of studies concerning confined systems deal with single molecules, ions, or atoms and focus on the influence of the confinement to the geometry 14,18,20 or electronic structure [10][11][12][13]18,19,21 of the confined system. There are only a few articles [14][15][16] where the influence of the confinement to the hydrogen-bonded system is investigated.…”

Section: Resultsmentioning

confidence: 99%

“…One possibility of modeling this effect is by using different analytic confining potentials. 9,15,[17][18][19][20] The advantage of their use is a large flexibility of their mathematical shape. They, however, do not take into account the granularity of the chemical environment and thus do not correspond the true chemical situation.…”

Section: Introductionmentioning

confidence: 99%

Influence of Confinement on Hydrogen Bond Energy. The Case of the FH···NCH Dimer

Jabłoński

Solà

2010

J. Phys. Chem. A

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The influence of the external pressure on the energy of the intermolecular hydrogen bond is investigated by modeling the pressure effects with helium atoms located at fixed points in space around the hydrogen bonded dimer. Several methods of estimating the energy of the H···N hydrogen bond in the He···FH···NCH···He model system are proposed. They show that the energy of the H···N hydrogen bond in this confined dimer decreases continuously with the reduction of the He···He distance, thus with the increase of the pressure effect exerted on the confined dimer.

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“…In a series of papers, Diercksen et al studied the electronic states and their density for low‐lying states of atoms and diatomic molecules confined by harmonic oscillator potentials . They looked for different degrees of confinement varying the frequency of the oscillator.…”

Section: Introductionmentioning

confidence: 99%

Electronic structure of first and second row atoms under harmonic confinement

Robles‐Navarro

Fuentealba

Muñoz

et al. 2019

Int J of Quantum Chemistry

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Atoms under pressure undergo a number of modifications of their electronic structure. Good examples are the spontaneous ionization, stabilization of excited‐state configurations, and contraction of atomic‐shells. In this work, we study the effects of confinement with harmonic potentials on the electronic structure of atoms from H to Ne. Dynamic and static correlation is taken into account with coupled cluster with single and double excitations and CASSCF calculations. Because the strength of harmonic confinement cannot be translated into pressure, we envisioned a “calibration” method to transform confinement into pressure. We focused on the effect of confinement on: (a) changes of electron distribution and localization within the K and L shells, (b) confinement‐induced ionization pressure, (c) level crossing of electronic states, and (d) correlation energy. We found that contraction of valence and core‐shells are not negligible and that the use of standard pseudopotentials might be not adequate to study solids under extreme pressures. The critical pressure at which atoms ionize follows a periodic trend, and it ranges from 28 GPa for Li to 10.8 TPa for Ne. In Li and Be, pressure induces mixing of the ground state configuration with excited states. At high pressure, the ground states of Li and Be become a doublet and a triplet with configurations 1s22p and 1s22s2p, respectively, which could change the chemistry of Be. Finally, it is observed that atoms with fewer electrons correlation increases, but for atoms with more electrons, the increasing of kinetic energy dominates over electron correlation.

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Quantum chemistry of confined systems: structure and vibronic spectra of a confined hydrogen molecule

Cited by 66 publications

References 11 publications

On the particular importance of vibrational contributions to the static electrical properties of model linear molecules under spatial confinement

On the particular importance of vibrational contributions to the static electrical properties of model linear molecules under spatial confinement

Influence of Confinement on Hydrogen Bond Energy. The Case of the FH···NCH Dimer

Electronic structure of first and second row atoms under harmonic confinement

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