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Botschwina, Peter; Bargholz, Arne; Sebald, Peter; Stein, Christopher J.; Oswald, Rainer

doi:10.1016/j.jms.2014.11.005

Cited by 5 publications

(5 citation statements)

References 39 publications

(68 reference statements)

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“…Relative (Q)-(T) is quite significant for all three properties, with values of −6.7 and −10.8 cm −1 for ω 1 and ω 3 , respectively. As is usually observed (see e.g., [27,28]), inclusion of relative Q-(Q) leads to a slight contraction of R e and a minor, but significant extension of ω 1 and ω 3 . The total composite R e value is only 0.0003Å larger than the employed reference structure.…”

Section: Electronic Structure Calculationssupporting

confidence: 64%

“…The determination of spectroscopic parameters and the generation of stick spectra can be performed automatically. The good performance of the program has recently been demonstrated in several papers [27,28,[36][37][38]. Employing a one-dimensional contraction scheme for the symmetric stretching and the bending vibrational coordinates and the use of prediagonalisation techniques when diagonalising the Hamiltonian matrix enable us to calculate the rovibrational term energies of the states of interest within some hundredths of a wavenumber or better compared to the results obtained by RVIB3.…”

Section: Rovibrational Calculationsmentioning

confidence: 98%

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Theoretical rovibrational spectroscopy beyond fc-CCSD(T): the cation CNC⁺

2015

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An accurate near-equilibrium potential energy surface (PES) for CNC + is constructed based on a high-level composite ab initio method. By combining explicitly correlated all-electron CCSD(T)-F12b with scalar relativistic effects and higher order correlation up to coupled cluster theory with singles, doubles, triples and quadruples (CCSDTQ) we achieve convergence in the wavenumbers of the fundamentals to ca. 1 cm −1 . Rovibrational energies are calculated in a variational approach and vibrational term energies and rotational constants are in excellent agreement with available experimental data. Accurate values for centrifugal distortion constants of CNC + in different vibrational states are predicted. Especially the centrifugal distortion constants in the vibrational ground state of D 0 = 0.563 · 10 −6 cm −1 and H 0 = 0.188 · 10 −10 cm −1 should be superior to experimentally derived values. Reassignments of some experimentally observed transitions are suggested based on a comparison of experimental and calculated term differences. The bending part of the PES appears to be almost quartic and the band origin of the bending vibration is predicted at 94.2 cm −1 . Absolute line intensities are calculated for various transitions in CNC + . For the bending vibration, an intensity is predicted that is three orders of magnitude smaller than for the antisymmetric stretching vibration.

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Section: Electronic Structure Calculationssupporting

confidence: 64%

Section: Rovibrational Calculationsmentioning

confidence: 98%

Theoretical rovibrational spectroscopy beyond fc-CCSD(T): the cation CNC⁺

2015

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“…Effects due to HC only show a slight dependence on the CH-stretch whereas they are still significant for ∆R and act in the opposite direction of the CV contribution. These trends are in line with what has been observed previously [44][45][46][47][48][49][50][51][52][53]. In case of the bending motion (inset lower panel) it is clear that the inclusion of (Q)-(T) is important with a contribution of about −58 cm −1 at 60 • .…”

Section: Construction Of the Pes And Edmssupporting

confidence: 91%

“…Spectroscopic parameters for additional selected rovibrational states in H 12 C 12 C − are provided in Table S6 of the Supplementary Materials. Based on previous experience with similar molecules [46,47,[49][50][51][52] the vibrational term energies G v are expected to be accurate to within 1 cm −1 and rotational parameters should display the same level of accuracy as observed for the vibrational ground state. Comparing the variational results for G v in H 12 C 12 C − with the corresponding composite VPT2 values for ν i in Table 5 almost perfect agreement can be observed as expected for a semi-rigid molecule.…”

Section: Results Of Variational Calculationsmentioning

confidence: 94%

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Ab Initio Rovibrational Spectroscopy of the Acetylide Anion

Schröder

2023

Molecules

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In this work the rovibrational spectrum of the acetylide anion HCC− is investigated using high-level electronic structure methods and variational rovibrational calculations. Using a composite approach the potential energy surface and dipole surface is constructed from explicitly correlated coupled-cluster accounting for corrections due to core-valence correlation, scalar relativistic effects and higher-order excitation effects. Previous approaches for approximating the latter are critically evaluated. Employing the composite potential, accurate spectroscopic parameters determined from variational calculations are presented. In comparison to the few available reference data the present results show excellent agreement with ground state rotational constants within 0.005% of the experimental value. Intensities determined from the variational calculations suggest the bending fundamental transition ν2 around 510 cm−1 to be the best target for detection. The rather weak CD stretching fundamental ν1 in deuterated isotopologues show a second-order resonance with the (0,20,1) state and the consequences are discussed in some detail. The spectroscopic parameters and band intensities provided for a number of vibrational bands in isotopologues of the acetylide anion should facilitate future spectroscopic investigations.

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