Theoretical study of molecular properties of low-lying electronic excited states of H<sub>2</sub>O and H<sub>2</sub>S

Páleníková, Jana; Kraus, Michal; Neogrády, Pavel; Kellö, Vladimı́r; Urban, Miroslav

doi:10.1080/00268970802454786

Cited by 30 publications

(42 citation statements)

References 64 publications

(89 reference statements)

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“…As water, hydrogen sulfide was also the subject of several high-level theoretical investigation, 103,[112][113][114] which are necessary, as there are rather few experimental data available for the lowest Rydberg states of H 2 S, 101,102,115,116 especially no accurate value could be measured for the first 1 A 2 state. As can be seen in Table 1, for a given basis set all tested CC methods provide very similar results, systematically within 0.01 eV of the exFCI results.…”

Section: Water Hydrogen Sulfide Ammonia and Hydrogen Chloridementioning

confidence: 99%

A Mountaineering Strategy to Excited States: Highly Accurate Reference Energies and Benchmarks

Loos

Scemama

Blondel

et al. 2018

J. Chem. Theory Comput.

300

100

645

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Striving to define very accurate vertical transition energies, we perform both high-level coupled cluster (CC) calculations (up to CCSDTQP) and selected configuration interaction (sCI) calculations (up to several millions of determinants) for 18 small compounds (water, hydrogen sulfide, ammonia, hydrogen chloride, dinitrogen, carbon monoxide, acetylene, ethylene, formaldehyde, methanimine, thioformaldehyde, acetaldehyde, cyclopropene, diazomethane, formamide, ketene, nitrosomethane, and the smallest streptocyanine). By systematically increasing the order of the CC expansion, the number of determinants in the CI expansion as well as the size of the one-electron basis set, we have been able to reach near full CI (FCI) quality transition energies. These calculations are carried out on CC3/ aug-cc-pVTZ geometries, using a series of increasingly large atomic basis sets systematically including diffuse functions. In this way, we define a list of 110 transition energies for states of various characters (valence, Rydberg, n → π, π → π*, singlet, triplet, etc.) to be used as references for further calculations. Benchmark transition energies are provided at the aug-cc-pVTZ level as well as with additional basis set corrections, in order to obtain results close to the complete basis set limit. These reference data are used to benchmark a series of 12 excited-state wave function methods accounting for double and triple contributions, namely ADC(2), ADC(3), CIS(D), CIS(D), CC2, STEOM-CCSD, CCSD, CCSDR(3), CCSDT-3, CC3, CCSDT., and CCSDTQ. It turns out that CCSDTQ yields a negligible difference with the extrapolated CI values with a mean absolute error as small as 0.01 eV, whereas the coupled cluster approaches including iterative triples are also very accurate (mean absolute error of 0.03 eV). Consequently, CCSDT-3 and CC3 can be used to define reliable benchmarks. This observation does not hold for ADC(3) that delivers quite large errors for this set of small compounds, with a clear tendency to overcorrect its second-order version, ADC(2). Finally, we discuss the possibility to use basis set extrapolation approaches so as to tackle more easily larger compounds.

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Section: Water Hydrogen Sulfide Ammonia and Hydrogen Chloridementioning

confidence: 99%

A Mountaineering Strategy to Excited States: Highly Accurate Reference Energies and Benchmarks

Loos

Scemama

Blondel

et al. 2018

J. Chem. Theory Comput.

300

100

645

View full text Add to dashboard Cite

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“…Only electric excess properties of small systems such as water molecule [4,5], hydrogen sulfide [6] and acetone [7] were examined thoroughly using advanced quantum chemical methods including electron correlation effects and the multi-configurational character of the excited states like CASSCF/CASPT2 [4,6] or coupled cluster (CC) [7] methods. The main conclusion that can be drawn from these calculations is that the electric excess properties are strongly state-dependent and can reach high values.…”

Section: Introductionmentioning

confidence: 99%

Electric properties of the low-lying excited states of benzonitrile: geometry relaxation and solvent effects

2015

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“…Our TBE/CBS of 0.72±0.02 D is slightly larger than the best previous estimate we have found (0.65 D). 99 The transition energy to the second ES, of 𝐵 1 symmetry, is also basis set sensitive, although in that case larger bases yield larger (and not smaller) transition energies, as shown in Table 3. Our TBE/CBS of 6.33±0.01 eV is close to previous estimates, 5,99,105 and also consistent with measurements, 107 although we recall that such comparisons should be made with care.…”

Section: H 2 O and H 2 Smentioning

confidence: 94%

“…99 The transition energy to the second ES, of 𝐵 1 symmetry, is also basis set sensitive, although in that case larger bases yield larger (and not smaller) transition energies, as shown in Table 3. Our TBE/CBS of 6.33±0.01 eV is close to previous estimates, 5,99,105 and also consistent with measurements, 107 although we recall that such comparisons should be made with care. The dipole moment of the 𝐵 1 state is very large and relatively insensitive to the basis set as compared to its 𝐴 2 counterpart.…”

Section: H 2 O and H 2 Smentioning

confidence: 94%

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.

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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 (

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Theoretical study of molecular properties of low-lying electronic excited states of H₂O and H₂S

Cited by 30 publications

References 64 publications

A Mountaineering Strategy to Excited States: Highly Accurate Reference Energies and Benchmarks

A Mountaineering Strategy to Excited States: Highly Accurate Reference Energies and Benchmarks

Electric properties of the low-lying excited states of benzonitrile: geometry relaxation and solvent effects

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

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Theoretical study of molecular properties of low-lying electronic excited states of H2O and H2S

Cited by 30 publications

References 64 publications

A Mountaineering Strategy to Excited States: Highly Accurate Reference Energies and Benchmarks

A Mountaineering Strategy to Excited States: Highly Accurate Reference Energies and Benchmarks

Electric properties of the low-lying excited states of benzonitrile: geometry relaxation and solvent effects

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

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Theoretical study of molecular properties of low-lying electronic excited states of H₂O and H₂S