Choosing an atomic basis set for TD-DFT, SOPPA, ADC(2), CIS(D), CC2 and EOM-CCSD calculations of low-lying excited states of organic dyes

Laurent, Adèle D.; Blondel, Aymeric; Jacquemin, Denis

doi:10.1007/s00214-015-1676-9

Cited by 29 publications

(30 citation statements)

References 62 publications

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“…The impact of using a smaller atomic basis set with CIS(D), ADC(2), and CC2 is beyond our scope here as such considerations can be found elsewhere. 131 …”

Section: Methodsmentioning

confidence: 99%

0–0 Energies Using Hybrid Schemes: Benchmarks of TD-DFT, CIS(D), ADC(2), CC2, and BSE/GW formalisms for 80 Real-Life Compounds

Jacquemin

Duchemin

Blase

2015

J. Chem. Theory Comput.

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223

244

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The 0–0 energies of 80 medium and large molecules have been computed with a large panel of theoretical formalisms. We have used an approach computationally tractable for large molecules, that is, the structural and vibrational parameters are obtained with TD-DFT, the solvent effects are accounted for with the PCM model, whereas the total and transition energies have been determined with TD-DFT and with five wave function approaches accounting for contributions from double excitations, namely, CIS(D), ADC(2), CC2, SCS-CC2, and SOS-CC2, as well as Green’s function based BSE/GW approach. Atomic basis sets including diffuse functions have been systematically applied, and several variations of the PCM have been evaluated. Using solvent corrections obtained with corrected linear-response approach, we found that three schemes, namely, ADC(2), CC2, and BSE/GW allow one to reach a mean absolute deviation smaller than 0.15 eV compared to the measurements, the two former yielding slightly better correlation with experiments than the latter. CIS(D), SCS-CC2, and SOS-CC2 provide significantly larger deviations, though the latter approach delivers highly consistent transition energies. In addition, we show that (i) ADC(2) and CC2 values are extremely close to each other but for systems absorbing at low energies; (ii) the linear-response PCM scheme tends to overestimate solvation effects; and that (iii) the average impact of nonequilibrium correction on 0–0 energies is negligible.

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“…The impact of using a smaller atomic basis set with CIS(D), ADC(2), and CC2 is beyond our scope here as such considerations can be found elsewhere. 131 …”

Section: Methodsmentioning

confidence: 99%

0–0 Energies Using Hybrid Schemes: Benchmarks of TD-DFT, CIS(D), ADC(2), CC2, and BSE/GW formalisms for 80 Real-Life Compounds

Jacquemin

Duchemin

Blase

2015

J. Chem. Theory Comput.

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223

244

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“…The B3LYP functional is known to give emission energy values close to experiment for fireflies (Berraud-Pache and Navizet, 2016 ). Finally, the basis set used is the 6-311G(2d,p) as used in previous publications (Laurent et al, 2015 ; Berraud-Pache and Navizet, 2016 ).…”

Section: Methodsmentioning

confidence: 99%

Modeling Chemical Reactions by QM/MM Calculations: The Case of the Tautomerization in Fireflies Bioluminescent Systems

2018

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In less than half a century, the hybrid QM/MM method has become one of the most used technique to model molecules embedded in a complex environment. A well-known application of the QM/MM method is for biological systems. Nowadays, one can understand how enzymatic reactions work or compute spectroscopic properties, like the wavelength of emission. Here, we have tackled the issue of modeling chemical reactions inside proteins. We have studied a bioluminescent system, fireflies, and deciphered if a keto-enol tautomerization is possible inside the protein. The two tautomers are candidates to be the emissive molecule of the bioluminescence but no outcome has been reached. One hypothesis is to consider a possible keto-enol tautomerization to treat this issue, as it has been already observed in water. A joint approach combining extensive MD simulations as well as computation of key intermediates like TS using QM/MM calculations is presented in this publication. We also emphasize the procedure and difficulties met during this approach in order to give a guide for this kind of chemical reactions using QM/MM methods.

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“…However, it has a clear tendency to overestimate transition energies, especially for Rydberg states, and it makes comparisons between methods more difficult as basis set dependencies are significantly different in wave function-based and density-based methods. 60 Let us now briefly review these efforts. In 2013, Watson et al obtained with the TZVP basis set and CCSDT-3 -a method employing an iterative approximation of the triples -transition energies very similar to the CC3 values.…”

Section: Introductionmentioning

confidence: 99%

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

Loos

Scemama

Blondel

et al. 2018

J. Chem. Theory Comput.

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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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Choosing an atomic basis set for TD-DFT, SOPPA, ADC(2), CIS(D), CC2 and EOM-CCSD calculations of low-lying excited states of organic dyes

Cited by 29 publications

References 62 publications

0–0 Energies Using Hybrid Schemes: Benchmarks of TD-DFT, CIS(D), ADC(2), CC2, and BSE/GW formalisms for 80 Real-Life Compounds

0–0 Energies Using Hybrid Schemes: Benchmarks of TD-DFT, CIS(D), ADC(2), CC2, and BSE/GW formalisms for 80 Real-Life Compounds

Modeling Chemical Reactions by QM/MM Calculations: The Case of the Tautomerization in Fireflies Bioluminescent Systems

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

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