Identification of Plasmons in Molecules with Scaled Ab Initio Approaches

Krauter, Caroline M.; Bernadotte, Stephan; Jacob, Christoph R.; Pernpointner, Markus; Dreuw, Andreas

doi:10.1021/acs.jpcc.5b07659

Cited by 40 publications

(120 citation statements)

References 83 publications

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Section: Soppa(scs-mp2) and Soppa(sos-mp2)mentioning

confidence: 73%

“…We note in this context that Kánná and Szalay recently reported [23] an even smaller deviation for CC2, 0.04 ± 0.012 eV, but they included only states with more than 80% single excitation character in contrast to our studies. Furthermore, in SOPPA(SOS-MP2), the excitation energies are decreased similarly to ISR-SOS-ADC(2) [12].…”

Section: Singlet Excitation Energies With the Tzvp Basis Setmentioning

confidence: 95%

“…SCS-CIS(D) [58,59] and SOS-CIS(D) [59], SCS-CC2 and SOS-CC2 [60] or SOS-ADC(2) [12,60,61]. A comparison between ADC(2) and SOS-ADC(2) for a subset of the benchmark set employed in this study showed significant differences in the mean errors between ADC(2) and two different versions of SOS-ADC(2) [12]. One of them [61] gives on average 0.16 eV larger excitation energies to singlet states than the original ADC(2), while in the intermediate state representation ISR-SOS-ADC(2) [12], where only the MP ground state wavefunction correlation coefficients are scaled, it predicts 0.2 eV lower excitation energies on average.…”

Section: Soppa(scs-mp2) and Soppa(sos-mp2)mentioning

confidence: 99%

“…a larger number of outliers. All SOPPA methods perform worse than ADC(2), for which a mean error of 0.01 ± 0.08 eV was reported for a slightly smaller subset of the benchmark set [12]. Table 7, SOPPA/TZVP and SOPPA(CCSD)/TZVP results for 71 excited triplet states of 20 molecules are presented together with the corresponding CC3/TZVP results [17].…”

Section: Singlet Excitation Energies With the Aug-cc-pvtz Basis Set Inmentioning

confidence: 99%

“…The performance of these methods in the calculation of vertical electronic excitation energies or even 0-0 transitions is well documented for ADC (2) [10][11][12][13][14][15][16] and CC2 [10,11,[17][18][19][20][21][22][23][24] but not for SOPPA. Vertical electronic excitation energies * Corresponding author.…”

Section: Introductionmentioning

confidence: 99%

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Performance of SOPPA-based methods in the calculation of vertical excitation energies and oscillator strengths

et al. 2015

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We present two new modifications of the second-order polarization propagator approximation (SOPPA), SOPPA(SCS-MP2) and SOPPA(SOS-MP2), which employ either spin-component-scaled or scaled opposite-spin MP2 correlation coefficients instead of the regular MP2 coefficients. The performance of these two methods, the original SOPPA method as well as SOPPA(CCSD) and RPA(D) in the calculation of vertical electronic excitation energies and oscillator strengths is investigated for a large benchmark set of 28 medium-sized molecules with 139 singlet and 71 triplet excited states. The results are compared with the corresponding CC3 and CASPT2 results from the literature for both the TZVP set and the larger and more diffuse aug-cc-pVTZ basis set. In addition, the results with the aug-cc-pVTZ basis set are compared with the theoretical best estimates for this benchmark set. We find that the original SOPPA method gives overall the smallest mean deviations from the reference values and the most consistent results

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Section: Soppa(scs-mp2) and Soppa(sos-mp2)mentioning

confidence: 73%

Section: Singlet Excitation Energies With the Tzvp Basis Setmentioning

confidence: 95%

Section: Soppa(scs-mp2) and Soppa(sos-mp2)mentioning

confidence: 99%

Section: Singlet Excitation Energies With the Aug-cc-pvtz Basis Set Inmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Performance of SOPPA-based methods in the calculation of vertical excitation energies and oscillator strengths

et al. 2015

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Electronic Rearrangement in Molecular Plasmons: An Electron Density and Electrostatic Potential‐Based Study

Paul

Balanarayan

2018

ChemPhysChem

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Plasmonic modes in single-molecule systems have been previously identified by scaling two-electron interactions in calculating excitation energies. Analysis of transition dipole moments for states of polyacenes based on configuration interaction is another method for characterising molecular plasmons. The principal features in the electronic absorption spectra of polyacenes are a low-intensity, lower-in-energy peak and a high-intensity, higher-in-energy peak. From calculations using time-dependent density functional theory with the B3LYP/cc-pVTZ basis set, both these peaks are found to result from the same set of electronic transitions, that is, HOMO-n to LUMO and HOMO to LUMO+n, where n varies as the number of fused rings increases. In this work, the excited states of polyacenes, naphthalene through pentacene, are analysed using electron densities and molecular electrostatic potential (MESP) topography. Compared to other excited states the bright and dark plasmonic states involve the least electron rearrangement. Quantitatively, the MESP topography indicates that the variance in MESP values and the displacement in MESP minima positions, calculated with respect to the ground state, are lowest for plasmonic states. The excited-state electronic density profiles and electrostatic potential topographies suggest the least electron rearrangement for the plasmonic states. Conversely, high electron rearrangement characterises a single-particle excitation. The molecular plasmon can be called an excited state most similar to the ground state in terms of one-electron properties. This is found to be true for silver (Ag ) and sodium (Na ) linear chains as well.

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Deciphering excited state properties utilizing algebraic diagrammatic construction schemes of decreasing order

Hoffmann

Dreuw

2021

J Comput Chem

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Excited state properties are difficult to trace back to the common molecular orbital picture when the excited state wavefunction is a linear combination of two or more Slater determinants. Here, a theoretical methodology is introduced based on the algebraic diagrammatic construction scheme for the polarization propagator (ADC(n)) that allows to make this connection and to eventually derive structure–function relationships. The usefulness of this approach is demonstrated by an analysis of the transition dipole moments of the low‐lying 1B3u and 2B3u states of anthracene and (1,4,5,8)‐tetraazaanthracene.

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Identification of Plasmons in Molecules with Scaled Ab Initio Approaches

Cited by 40 publications

References 83 publications

Performance of SOPPA-based methods in the calculation of vertical excitation energies and oscillator strengths

Performance of SOPPA-based methods in the calculation of vertical excitation energies and oscillator strengths

Electronic Rearrangement in Molecular Plasmons: An Electron Density and Electrostatic Potential‐Based Study

Deciphering excited state properties utilizing algebraic diagrammatic construction schemes of decreasing order

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