Excited Electronic States, Transition Probabilities, and Radiative Lifetimes of CAs: A Theoretical Contribution and Challenge to Experimentalists

Batista, Ana Paula de Lima; Oliveira-Filho, Antonio G. S. de; Ornellas, Fernando R.

doi:10.1021/jp204497p

Cited by 14 publications

(4 citation statements)

References 47 publications

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“…The single-reference CC hierarchy breaks down whenever a single determinant becomes an improper zeroth-order description of the system, whereas multireference methods lack a systematic hierarchy comparable to CC theory. The standard schemes, beyond second-order perturbation theory, still rely on multireference configuration interaction (MRCI) with approximate size-extensivity corrections. − The extension of coupled-cluster theory to multireference cases, on the other hand, is not straightforward, and only recently have a number of implementations been reported that are capable of treating realistic systems. − In this context, the multireference coupled-cluster (MRCC) theory , should provide a very reliable way to treat systems with such complex electronic structure.…”

Section: Introductionmentioning

confidence: 99%

How To Arrive at Accurate Benchmark Values for Transition Metal Compounds: Computation or Experiment?

Aoto

Batista

Köhn

et al. 2017

J. Chem. Theory Comput.

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129

165

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With the objective of analyzing which kind of reference data is appropriate for benchmarking quantum chemical approaches for transition metal compounds, we present the following, (a) a collection of 60 transition metal diatomic molecules for which experimentally derived dissociation energies, equilibrium distances, and harmonic vibrational frequencies are known and (b) a composite computational approach based on coupled-cluster theory with basis set extrapolation, inclusion of core-valence correlation, and corrections for relativistic and multireference effects. The latter correction was obtained from internally contracted multireference coupled-cluster (icMRCC) theory. This composite approach has been used to obtain the dissociation energies and spectroscopic constants for the 60 molecules in our data set. In accordance with previous studies on a subset of molecules, we find that multireference corrections are rather small in many cases and CCSD(T) can provide accurate reference values, if the complete basis set limit is explored. In addition, the multireference correction improves the results in cases where CCSD(T) is not a good approximation. For a few cases, however, strong deviations from experiment persist, which cannot be explained by the remaining error in the computational approach. We suggest that these experimentally derived values require careful revision. This also shows that reliable reference values for benchmarking approximate computational methods are not always easily accessible via experiment and accurate computations may provide an alternative way to access them. In order to assess how the choice of reference data affects benchmark studies, we tested 10 DFT functionals for the molecules in the present data set against experimental and calculated reference values. Despite the differences between these two sets of reference values, we found that the ranking of the relative performance of the DFT functionals is nearly independent of the chosen reference.

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Section: Introductionmentioning

confidence: 99%

How To Arrive at Accurate Benchmark Values for Transition Metal Compounds: Computation or Experiment?

Aoto

Batista

Köhn

et al. 2017

J. Chem. Theory Comput.

Self Cite

129

165

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show abstract

“…Other properties that have a smaller impact on cooling efficiency such as harmonic frequencies, spin-orbit splittings, and electronic energies were also predicted with comparable accuracy. A comparison between the predictions of the MRCISD+Q/aV5Z level of theory for the CAs molecule [32] and experimental measurements [33] shows that calculated bond lengths are within 1 pm of experimental values therefore the calculations for TeH + should be more accurate than the ones for SbH.…”

Section: Molecular Structurementioning

confidence: 87%

Optical Pumping of TeH+: Implications for Search for Varying mp/me

Stollenwerk¹,

Kokish²,

Oliveira-Filho³

et al. 2018

Preprint

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Molecular overtone transitions provide optical frequency transitions sensitive to variation in the proton-to-electron mass ratio (μ = mp/me). However, robust molecular state preparation presents a challenge critical for achieving high precision. Here, we characterize infrared and optical-frequency broadband laser cooling schemes for TeH+, a species with multiple electronic transitions amenable to sustained laser control. Using rate equations to simulate laser cooling population dynamics, we estimate the fractional sensitivity to μ attainable using TeH+. We find that laser cooling of TeH+ can lead to significant improvements on current μ variation limits.

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“…FCFs depend most strongly on the difference in equilibrium bond length between electronic states, and the equilibrium bond lengths for SbH were predicted to within 3 pm of the measured values. A comparison between the predictions of the MRCISD+Q/aV5Z level of theory for the CAs molecule [32] and experimental measurements [33] shows that calculated bond lengths are within 1 pm of experimental values; therefore, the calculations for TeH + should be more accurate than the ones for SbH. For optical cooling, we also rely on short lifetimes.…”

Section: Molecular Structurementioning

confidence: 94%

Optical Pumping of TeH+: Implications for the Search for Varying mp/me

Stollenwerk

Kokish

Oliveira-Filho

et al. 2018

Atoms

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Molecular overtone transitions provide optical frequency transitions sensitive to variation in the proton-to-electron mass ratio ( μ ≡ m p / m e ). However, robust molecular state preparation presents a challenge critical for achieving high precision. Here, we characterize infrared and optical-frequency broadband laser cooling schemes for TeH + , a species with multiple electronic transitions amenable to sustained laser control. Using rate equations to simulate laser cooling population dynamics, we estimate the fractional sensitivity to μ attainable using TeH + . We find that laser cooling of TeH + can lead to significant improvements on current μ variation limits.

show abstract

Excited Electronic States, Transition Probabilities, and Radiative Lifetimes of CAs: A Theoretical Contribution and Challenge to Experimentalists

Cited by 14 publications

References 47 publications

How To Arrive at Accurate Benchmark Values for Transition Metal Compounds: Computation or Experiment?

How To Arrive at Accurate Benchmark Values for Transition Metal Compounds: Computation or Experiment?

Optical Pumping of TeH<sup>+</sup>: Implications for Search for Varying <em>m<sub>p</sub></em>/<em>m<sub>e</sub></em>

Optical Pumping of TeH+: Implications for the Search for Varying mp/me

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