Photodissociation of ICl Molecule Oriented by an Intense Electric Field:  Experiment and Theoretical Analysis

Bazalgette, G.; White, Richard; Trénec, Gérard; Audouard, Éric; Büchner, Matthias; Vigué, J.

doi:10.1021/jp972074b

Cited by 19 publications

(20 citation statements)

References 61 publications

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“…[23][24][25] It complements a more venerable but less general method, which provides oriented beams in pure rotational states but works only for symmetric top molecules and requires use of long (∼1 m) inhomogeneous focusing fields. 26 The hydridization method is applicable to linear and asymmetric tops also and its experimental implementation merely requires installing a short (∼1 cm) pair of parallel electrodes or pole pieces.…”

Section: Prototypical Applicationsmentioning

confidence: 99%

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Manipulating Molecules via Combined Static and Laser Fields

1999

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Interaction of the strong electric field of an intense laser beam with the anisotropic polarizability of a linear molecule creates pendular states, superpositions of the field-free rotational states, in which the molecular axis librates about the field direction. Angular motion in the low-lying pendular states is thereby restricted by a double-well potential, governed by the laser intensity. The pendular energy levels occur as pairs of opposite parity, with separations corresponding to the frequency for tunneling between the wells. If the molecule is polar or paramagnetic, introducing a static electric or magnetic field connects the nearly degenerate pendular levels and thus induces strong pseudo-first-order Stark or Zeeman effects. This can be exploited in many schemes to control and manipulate molecular trajectories.

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Section: Prototypical Applicationsmentioning

confidence: 99%

“…This molecule has become a favorite test case for orientation techniques. 23 As its polarizability anisotropy parameter is large, high values of ∆ω are readily obtained. The pseudo-first-order effect thus can become extremely strong for a very weak static field (as in Figure 5).…”

Section: Prototypical Applicationsmentioning

confidence: 99%

Manipulating Molecules via Combined Static and Laser Fields

1999

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“…However such a measurement is not possible at this time for PtC because the electric field strength required for this approach cannot be obtained with the existing experimental arrangement. Photodissociation studies 29 have also recently been able to directly determine the sign of the ground state dipole moment of a molecule so in principle it is possible to completely map the magnitude and orientation of for the observed electronic states of a molecule experimentally.…”

Section: B Dipole Momentsmentioning

confidence: 99%

Laser-induced fluorescence and Optical/Stark spectroscopy of PtC

Beaton

Steimle

1999

The Journal of Chemical Physics

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Laser velocity modulation spectroscopy of the 3 Δ(3d4s)-X 3 Φ(3d 2 ) visible system of TiCl + and characterization of the spin-orbit structure Optical/Stark measurements have been performed on the ͑0,0͒ bands of both the AЉ 1 ⌺ ϩ -X 1 ⌺ ϩ system ( 0 Ϸ12 643 cm Ϫ1 ) and the AЈ 1 ⌸ -X ⌺ ϩ system ( 0 Ϸ13 196 cm Ϫ1 ) of platinum monocarbide. The PtC molecules were produced in a pulsed supersonic molecular beam source following the reaction of laser ablated platinum vapor with a mixture of a few percent of methane in argon. The newly determined permanent electric dipole moments obtained are 1.94(2)D (AЉ 1 ⌺ ϩ ) and 1.919(9)D (AЈ 1 ⌸). These results are discussed in terms of a proposed molecular orbital correlation diagram for platinum containing diatomics. The laser-induced fluorescence spectrum of the (0,0)AЉ 1 ⌺ ϩ -X 1 ⌺ ϩ transition of PtC has been re-recorded at high resolution ͑full width of half-maximum ϳ40 MHz͒ and analyzed to yield rotational constants for the four most abundant isotopomers of PtC, extending the previous analysis ͓Appelblad, Nilsson, and Scullman, Phys. Scr. 7, 65 ͑1973͔͒. The anomalously large value ͑ϳ15 MHz͒ for the newly derived nuclear-spin rotation parameter, C I ( 195 Pt), for the AЉ 1 ⌺ ϩ state is discussed.

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“…Strongly bound pendular states were realized by Block et al [3] in 1992, who measured infrared spectra of a linear HCN trimer in the 30 kV/ cm field and reported a drastic evolution of the spectra from that of a field-free condition. Thereafter, pendular states have been applied to many studies for steric effects of reactions [4], controls of molecular orientation [5][6][7][8][9][10][11], measurements of electric dipole moments [12][13][14][15], determinations of transition-dipole orientations [16,17], superfluid helium droplet spectroscopies [18][19][20][21][22][23], and so on [24][25][26][27][28].…”

Section: Introductionmentioning

confidence: 99%

Pendular-limit representation of energy levels and spectra of symmetric- and asymmetric-top molecules

Kanya

Ohshima

2004

Phys. Rev. A

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We report theoretical investigations pertaining to spectroscopy of pendular-state molecules, which are subjected to the large electrostatic interaction between the molecular dipole and a strong external field. After an appropriate coordinate transformation and a power-series expansion with an order parameter that represents the degree of pendular condition, the zeroth-order Hamiltonian for the pendular limit has been derived. Motions of asymmetric tops in a high field are well described as two-dimensional anisotropic harmonic oscillations, and pendular-state quantum numbers have been introduced to label the energy levels. By using perturbative treatments, energies up to the 0 order are represented analytically with the pendular-state quantum numbers. Symmetry considerations are also accomplished by using the group theory appropriate to dipolar rigid bodies of symmetric and asymmetric tops in a uniform electric field. Energy levels and wave functions are classified into irreducible representations of the groups and selection rules for optical transitions are described. Energy-level correlations between the field-free and pendular conditions are also discussed on the basis of the group theoretical considerations. For symmetric and asymmetric tops, pendular-limit selection rules on the quantum numbers are derived by expanding the transition-dipole operators on , and transition strengths are analytically evaluated for all the excitation configurations with each of the transition types. Utilities of the present formulation have been verified by the comparison with exact model calculations based on the matrix diagonalization with a free-rotation basis set.

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Photodissociation of ICl Molecule Oriented by an Intense Electric Field: Experiment and Theoretical Analysis

Cited by 19 publications

References 61 publications

Manipulating Molecules via Combined Static and Laser Fields

Manipulating Molecules via Combined Static and Laser Fields

Laser-induced fluorescence and Optical/Stark spectroscopy of PtC

Pendular-limit representation of energy levels and spectra of symmetric- and asymmetric-top molecules

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