Extended permutation-inversion groups for simultaneous treatment of the rovibronic states of trans-acetylene, cis-acetylene, and vinylidene

Hougen, Jon T.; Merer, A. J.

doi:10.1016/j.jms.2011.03.020

Cited by 18 publications

(66 citation statements)

References 25 publications

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“…For coupled identical benders, as in ABBA molecules, the states must be representations of the appropriate point group. The permutation-inversion formalism 50,51 has been forwarded as a robust method and a discussion of the symmetry operations used here is available, 32 so here we briefly review only the two operations used in this work. Operationally, we introduce two symmetry operations on the basis |n …”

Section: Coupled Identical Bendersmentioning

confidence: 99%

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A study of the bending motion in tetratomic molecules by the algebraic operator expansion method

Larese¹,

Caprio²,

Pérez‐Bernal³

et al. 2014

The Journal of Chemical Physics

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We study the bending motion in the tetratomic molecules C2H2 (˜X 1 + g ), C2H2 ( ˜A 1Au) trans-S1, C2H2 ( ˜A 1A2) cis-S1, and ˜X 1A1 H2CO. We show that the algebraic operator expansion method with only linear terms comprised of the basic operators is able to describe the main features of the level energies in these molecules in terms of two (linear) or three (trans-bent, cis-bent, and branched) parameters. By including quadratic terms, the rms deviation in comparison with experiment goes down to typically ∼10 cm−1 over the entire range of energy 0–6000 cm−1.We determine the parameters by fitting the available data, and from these parameters we construct the algebraic potential functions. Our results are of particular interest in high-energy regions where spectra are very congested and conventional methods, force-field expansions or Dunham-expansions plus perturbations, are difficult to apply

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Section: Coupled Identical Bendersmentioning

confidence: 99%

“…51,52 We identify the symmetry of the states on the basis of the eigenvalues of these operators. Note that, since the HamiltonianĤ is rotationally invariant, the total twodimensional angular momentum 12 = 1 + 2 is conserved.…”

Section: Coupled Identical Bendersmentioning

confidence: 99%

A study of the bending motion in tetratomic molecules by the algebraic operator expansion method

Larese¹,

Caprio²,

Pérez‐Bernal³

et al. 2014

The Journal of Chemical Physics

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show abstract

“…If isomerization through the torsional vibration is important, as in H 2 O 2 , there will be a further staggering of the K = 4n levels versus the K = 4n + 2 levels. 30 Preliminary results suggest that this further staggering is not significant, 28 but it is clear that full analyses of the K-structure require data from K values up to 3 or possibly 4.…”

Section: Introductionmentioning

confidence: 98%

“…The first is a tunneling splitting between equivalent structures differing only in the bending angles at the two ends of the molecule. For group theoretical reasons, 30 this produces an even-odd staggering of the K-structure of a vibrational level. In addition, interactions occur between cis and trans levels at similar energies.…”

Section: Introductionmentioning

confidence: 99%

“…In addition, interactions occur between cis and trans levels at similar energies. 18,28,30 These are the mechanisms by which the cis levels obtain their intensity by mixing with nearby trans levels, though the selection rules and level shifts are different for even and odd K-values. Combining these two effects, the resulting K-staggering varies in a seemingly random fashion from level to level.…”

Section: Introductionmentioning

confidence: 99%

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Probing cis-trans isomerization in the S1 state of C2H2 via H-atom action and hot band-pumped IR-UV double resonance spectroscopies

Changala

Baraban

Merer

et al. 2015

The Journal of Chemical Physics

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Articles you may be interested inVibrational energy relaxation of benzene dimer and trimer in the CH stretching region studied by picosecond time-resolved IR-UV pump-probe spectroscopy J. Chem. Phys. 136, 044304 (2012) Probing cis-trans isomerization in the S 1 state of C 2 H 2 via H-atom action and hot band-pumped IR-UV double resonance spectroscopies We report novel experimental strategies that should prove instrumental in extending the vibrational and rotational assignments of the S 1 state of acetylene, C 2 H 2 , in the region of the cis-trans isomerization barrier. At present, the assignments are essentially complete up to ∼500 cm −1 below the barrier. Two difficulties arise when the assignments are continued to higher energies. One is that predissociation into C 2 H + H sets in roughly 1100 cm −1 below the barrier; the resulting quenching of laser-induced fluorescence (LIF) reduces its value for recording spectra in this region. The other difficulty is that tunneling through the barrier causes a staggering in the K-rotational structure of isomerizing vibrational levels. The assignment of these levels requires data for K values up to at least 3. Given the rotational selection rule K ′ − ℓ ′′ = ±1, such data must be obtained via excited vibrational levels of the ground state with ℓ ′′ > 0. In this paper, high resolution H-atom resonance-enhanced multiphoton ionization spectra are demonstrated to contain predissociated bands which are almost invisible in LIF spectra, while preliminary data using a hyperthermal pulsed nozzle show that ℓ ′′ = 2 states can be selectively populated in a jet, giving access to K ′ = 3 states in IR-UV double resonance. C 2015 AIP Publishing LLC. [http://dx

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Multi-valued versus single-valued large-amplitude bending-torsional–rotational coordinate systems for simultaneously treating trans-bent and cis-bent acetylene in its S1 state

Extended permutation-inversion groups for simultaneous treatment of the rovibronic states of trans-acetylene, cis-acetylene, and vinylidene

Cited by 18 publications

References 25 publications

A study of the bending motion in tetratomic molecules by the algebraic operator expansion method

A study of the bending motion in tetratomic molecules by the algebraic operator expansion method

Probing cis-trans isomerization in the S1 state of C2H2 via H-atom action and hot band-pumped IR-UV double resonance spectroscopies

Multi-valued versus single-valued large-amplitude bending-torsional–rotational coordinate systems for simultaneously treating trans-bent and cis-bent acetylene in its S1 state

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