New diagnostics for coupled-cluster and Møller–Plesset perturbation theory

Janssen, Curtis L.; Nielsen, Ida M. B.

doi:10.1016/s0009-2614(98)00504-1

Cited by 326 publications

(337 citation statements)

References 18 publications

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“…The diagnostic criteria proposed by Janssen and Nielsen 47 and implemented in the Turbomole program do not indicate a considerable multireference character of the ground state. The obtained values are below or very close to the optimal accepted values of 0.015 and 0.030 for the D1 (MP2) and D1(CC2) diagnostic criteria, respectively.…”

Section: Optical Absorption Propertiesmentioning

confidence: 92%

Ab initio description of photoabsorption and electron transfer in a doubly‐linked porphyrin‐fullerene dyad

et al. 2008

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Structure, photoabsorption and excited states of two representative conformations obtained from molecular dynamics (MD) simulations of a doubly-linked porphyrin-fullerene dyad DHD6ee are studied by using both DFT and wavefunction based methods. Charge transfer from the donor (porphyrin) to the acceptor (fullerene) and the relaxation of the excited state are of special interest. The results obtained with LDA, GGA, and hybrid functionals (SVWN, PBE, and B3LYP, respectively) are analyzed with emphasis on the performance of used functionals as well as from the point of view of their comparison with wavefunction based methods (CCS, CIS(D), and CC2). Characteristics of the MD structures are retained in DFT optimization. The relative orientation of porphyrin and fullerene is significantly influencing the MO energies, the charge transfer (CT) in the ground state of the dyad and the excitation of ground state CT complex (g-CTC). At the same time, the excitation to the locally excited state of porphyrin is only little influenced by the orientation or cc distance. TD-DFT underestimates the excitation energy of the CT state, however for some cases (with relatively short donor-acceptor separations), the use of a hybrid functional like B3LYP alleviates the problem. Wavefunction based methods and CC2 in particular appear to overestimate the CT excitation energies but the inclusion of proper solvation models can significantly improve the results.

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Section: Optical Absorption Propertiesmentioning

confidence: 92%

Ab initio description of photoabsorption and electron transfer in a doubly‐linked porphyrin‐fullerene dyad

et al. 2008

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“…29,57 To this end, Table 2 shows the complete set (96 excited states, nine methods) of calculated ΔE 00 energies. Furthermore, for each group of molecules as well as for data sets containing either all of the 96 excited states or all systems in groups I-III (inorganic molecules) and groups IV-IX (organic molecules), for the inorganic molecules is likely to reflect the relative unimportance of multireference correlation effects for most of the organic excited states studied, whereas for the inorganic systems, at least a few states (e.g., the 1 1 Π state of SiO 86 ) have some double-excitation character or are populated from a multi-reference ground state (as identifiable by various diagnostics [87][88][89] excitation energies compared with experimental absorption maxima, the full inclusion of geometric relaxation effects may render the present analysis oppositely inclined, despite that the comparison is here with experimental ΔE 00 energies.…”

Section: δE 00 Energies With Different Methodsmentioning

confidence: 99%

How Method-Dependent Are Calculated Differences between Vertical, Adiabatic, and 0–0 Excitation Energies?

2014

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ABSTRACT:Through a large number of benchmark studies, the performance of different quantum chemical methods in calculating vertical excitation energies is today quite well established. Furthermore, these efforts have in recent years been complemented by a few benchmarks focusing instead on adiabatic excitation energies. However, it is much less well established how calculated differences between vertical, adiabatic and 0-0 excitation energies vary between methods, which may be due to the cost of evaluating zero-point vibrational energy corrections for excited states. To fill this gap, we have calculated vertical, adiabatic and 0-0 excitation energies for a benchmark set of molecules covering both organic and inorganic systems. Considering in total 96 excited states and using both TD-DFT with a variety of exchange-correlation functionals and the ab initio CIS and CC2 methods, it is found that while the vertical excitation energies obtained with the various methods show an average (over the 96 states) standard deviation of 0.39 eV, the corresponding standard deviations for the differences between vertical, adiabatic and 0-0 excitation energies are much smaller: 0.10 (difference between adiabatic and vertical) and 0.02 eV (difference between 0-0 and adiabatic). These results provide a quantitative measure showing that the calculation of such quantities in photochemical modeling is well amenable to low-level methods. In addition, we also report on how these energy differences vary between chemical systems and assess the performance of TD-DFT, CIS and CC2 in reproducing experimental 0-0 excitation energies.

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“…The structures were optimized and, subsequently, excitation energies and intensities were calculated. These CC2 calculations yielded results, but they were problematic because the values for the D 1 diagnostics [29] (0.14 for 5 and 0.08 for btmgb) clearly lie outside the range (D 1 A C H T U N G T R E N N U N G (CC2) = 0.05) over which the method can be expected to perform well. The spectra obtained are shown in the Supporting Information.…”

Section: H T U N G T R E N N U N G (Dmso)]mentioning

confidence: 99%

Mono‐ and Diprotonation of the Superbasic Bisguanidine 1,2‐Bis(N,N,N′,N′‐tetramethylguanidino)benzene (btmgb) and Pt^II and Pt^IV Complexes of Chelating Bisguanidines and Guanidinates

Peters

Wild

Hübner

et al. 2008

Chemistry A European J

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New Pt complexes of chelating bisguanidines and guanidinate ligands were synthesized and characterized. 1,2-Bis(N,N,N',N'-tetramethylguanidino)benzene (btmgb) was used as a neutral chelating bisguanidine ligand, and 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate (hpp(-)) as a guanidinate ligand. The salts [btmgbH]+[HOB(C6F5)3](-) and [btmgbH2]Cl2 and the complexes [(btmgb)PtCl2], [(btmgb)PtCl(dmso)]+[PtCl3(dmso)](-), and [(btmgb)PtCl(dmso)]+[Cl(-)] were synthesized and characterized. In the [btmgbH]+ cation the proton is bound to only one N atom. In the other complexes, both imine N atoms are coordinated to the Pt II, thus adopting a eta2-coordinational mode. The hpp(-) anion, which usually prefers a bridging binding mode in dinuclear complexes, is eta2-coordinated in the Pt IV complex [(eta2-hpp)(hppH)PtCl2(N(H)C(O)CH3)], which is formed (in low yield) by reaction between cis-[(hppH)2PtCl2] and H2O2 in CH3CN.

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New diagnostics for coupled-cluster and Møller–Plesset perturbation theory

Cited by 326 publications

References 18 publications

Ab initio description of photoabsorption and electron transfer in a doubly‐linked porphyrin‐fullerene dyad

Ab initio description of photoabsorption and electron transfer in a doubly‐linked porphyrin‐fullerene dyad

How Method-Dependent Are Calculated Differences between Vertical, Adiabatic, and 0–0 Excitation Energies?

Mono‐ and Diprotonation of the Superbasic Bisguanidine 1,2‐Bis(N,N,N′,N′‐tetramethylguanidino)benzene (btmgb) and Pt^II and Pt^IV Complexes of Chelating Bisguanidines and Guanidinates

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New diagnostics for coupled-cluster and Møller–Plesset perturbation theory

Cited by 326 publications

References 18 publications

Ab initio description of photoabsorption and electron transfer in a doubly‐linked porphyrin‐fullerene dyad

Ab initio description of photoabsorption and electron transfer in a doubly‐linked porphyrin‐fullerene dyad

How Method-Dependent Are Calculated Differences between Vertical, Adiabatic, and 0–0 Excitation Energies?

Mono‐ and Diprotonation of the Superbasic Bisguanidine 1,2‐Bis(N,N,N′,N′‐tetramethylguanidino)benzene (btmgb) and PtII and PtIV Complexes of Chelating Bisguanidines and Guanidinates

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Mono‐ and Diprotonation of the Superbasic Bisguanidine 1,2‐Bis(N,N,N′,N′‐tetramethylguanidino)benzene (btmgb) and Pt^II and Pt^IV Complexes of Chelating Bisguanidines and Guanidinates