<i>Ab initio</i> study of low-lying excited states of HCl: Accurate calculations of optical valence-shell excitations

Engin, Selma; Sisourat, Nicolas; Carniato, S.

doi:10.1063/1.4757725

Cited by 16 publications

(10 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The dipole transition moments used to compute the effective operators α Σ ( R ) and α Π ( R ) are shown in Figure . PES and dipole transition moments of HCl are discussed in more detail in ref . The nature of the low-lying excited states of HCl is discussed in refs and − .…”

Section: Methodsmentioning

confidence: 99%

Raman Chirped Adiabatic Passage Probed by X-ray Spectroscopy

et al. 2013

Self Cite

View full text Add to dashboard Cite

We report a theoretical study of the selective vibrational excitation of a HCl molecule achieved by Raman chirped adiabatic passage (RCAP) and probed by X-ray photoelectron spectroscopy (XPS). It is demonstrated that HCl can be prepared in any vibrational level up to ν = 9 with nearly complete population inversion. We explore the effects of both the rotation of the molecule and of the temperature on the RCAP process, which is proved to be very robust. Furthermore, we emphasize that XPS spectra at the chlorine K-shell threshold show characteristic signatures of the populated vibrational level, allowing us to follow the RCAP process.

show abstract

Section: Methodsmentioning

confidence: 99%

Raman Chirped Adiabatic Passage Probed by X-ray Spectroscopy

et al. 2013

Self Cite

View full text Add to dashboard Cite

show abstract

“… a Transition energies are in eV and dipoles in D. b Computed using CCSDTQ/aug-cc-pVTZ values and CCSDTQP/aug-cc-pVDZ corrections. Note that CCSDTQ is equivalent to FCI for BH. c See the Computational Methods section. d Average between the MR-ACPF/aug-cc-pCV7Z(i) values obtained for r = 1.220 and 1.225 Å in ref . e FCI/aug-cc-pVDZ value of ref . f CC2/aug-cc-pVQZ result from ref . g CCSD(T)/CBS value from ref . h CISDTQ/aug-cc-pCVQZ value from ref . A f value of 0.071 is also reported in Table 2 of the same work. i Stark (emission) measurements of ref . j f 00 obtained from laser-induced fluorescence in ref .…”

Section: Resultsmentioning

confidence: 93%

“… h CISDTQ/aug-cc-pCVQZ value from ref . A f value of 0.071 is also reported in Table 2 of the same work. …”

Section: Resultsmentioning

confidence: 95%

Mountaineering Strategy to Excited States: Highly Accurate Oscillator Strengths and Dipole Moments of Small Molecules

Chrayteh

Blondel

Loos

et al. 2020

J. Chem. Theory Comput.

View full text Add to dashboard Cite

This work presents a series of highly-accurate excited-state properties obtained using high-order coupledcluster (CC) calculations performed with a series of diffuse containing basis sets, as well as extensive comparisons with experimental values. Indeed, we have computed both the main ground-to-excited transition property, the oscillator strength, as well as the ground-and excited-state dipole moments, considering thirteen small molecules (hydridoboron, hydrogen chloride, water, hydrogen sulfide, boron fluoride, carbon monoxide, dinitrogen, ethylene, formaldehyde, thioformaldehyde, nitroxyl, fluorocarbene, and silylidene). We systematically include corrections up to the quintuple (CCSDTQP) in the CC expansion and extrapolate to the complete basis set limit. When comparisons with experimental measurements are possible, that is, when a number of consistent experimental data can be found, theory typically provides values falling within the experimental error bar for the excited-state properties. Besides completing our previous studies focussed on transition energies (

show abstract

“…In this case, the choice of using this combination of a PEC and a TDMC from two different sources has been validated by the comparison of our results with the experiments from different sources (Pezzella et al, 2021). All other PECs and TDMCs are taken from Engin et al (2012). The potentials are described using the cubic spline interpolation implemented in DUO.…”

Section: Potential Energy and Transition Dipole Moment Curvesmentioning

confidence: 95%

“…The double well structure of the B 1 Σ state arises from the avoided crossing between two states, identified as E 1 Σ + and V 1 Σ + , however, for the photodissociation process there is no advantage in treating the two states separately (Lefebvre- Brion et al, 2011). The potential energy curves from Engin et al (2012) were shifted to improve the agreement with the experimental results from Cheng et al (2002) and Li et al (2006) for the C 1 Π, D 1 Π, H 1 Σ + , K 1 Π, M 1 Π states; the B 1 Σ + , 5 1 Π and 4 1 Σ + are shifted in order to keep constant the energy differences with the surrounding states. The TDMCs are described by interpolation.…”

Section: Potential Energy and Transition Dipole Moment Curvesmentioning

confidence: 99%

ExoMol photodissociation cross sections I: HCl and HF

Pezzella,

Tennyson,

Yurchenko

2022

Preprint

View full text Add to dashboard Cite

Photon initiated chemistry, i.e. the interaction of light with chemical species, is a key factor in the evolution of the atmosphere of exoplanets. For planets orbiting stars in UV-rich environments, photodissociation induced by high energy photons dominates the atmosphere composition and dynamics. The rate of photodissociation can be highly dependent on atmospheric temperature, as increased temperature leads to increased population of vibrational excited states and the consequent lowering of the photodissociation threshold. This paper inaugurates a new series of papers presenting computed temperature-dependent photodissociation cross sections with rates generated for different stellar fields. Cross sections calculations are performed by solving the time-independent Schrödinger equation for each electronic state involved in the process. Here photodissociation cross sections for hydrogen chloride and hydrogen fluoride are computed for a grid of 34 temperatures between 0 and 10 000 K. Use of different radiation fields shows that for the Sun and cooler stars the photodissociation rate can increase exponentially for molecular temperatures above 1000 K; conversely the photodissociation rates in UV rich fields instead are almost insensitive to the temperature of the molecule. Furthermore, these rates show extreme sensitivity to the radiation model used for cool stars, suggesting that further work on these may be required. The provision of an ExoMol database of cross sections is discussed.

show abstract

Ab initio study of low-lying excited states of HCl: Accurate calculations of optical valence-shell excitations

Cited by 16 publications

References 31 publications

Raman Chirped Adiabatic Passage Probed by X-ray Spectroscopy

Raman Chirped Adiabatic Passage Probed by X-ray Spectroscopy

Mountaineering Strategy to Excited States: Highly Accurate Oscillator Strengths and Dipole Moments of Small Molecules

ExoMol photodissociation cross sections I: HCl and HF

Contact Info

Product

Resources

About