Time-Dependent Long-Range-Corrected Double-Hybrid Density Functionals with Spin-Component and Spin-Opposite Scaling: A Comprehensive Analysis of Singlet–Singlet and Singlet–Triplet Excitation Energies

Casanova-Páez, Marcos; Goerigk, Lars

doi:10.1021/acs.jctc.1c00535

Cited by 73 publications

(177 citation statements)

References 137 publications

(431 reference statements)

Supporting

Mentioning

171

Contrasting

Order By: Relevance

“…The inter-fragment interaction energy can be written as follows:

where

means the electronic preparation (or intra-fragment reference) energy and describes how much energy is necessary to bring the fragments into the electronic structure that is optimal for interaction,

, and

are the inter-fragment electrostatic and exchange contributions,

and

are the non-dispersive and dispersive parts of the correlation energy at the CCSD level, and

is the triples correction term to the inter-fragment interaction energy. The electronically excited states were also computed considering the SCS-PBE-QIDH XC functional ( Casanova-Páez and Goerigk, 2021 ) built as the spin-component scaled version of Adamo’s PBE-based double hybrid ( Brémond et al, 2014 ) optimized for excited states, all of them implemented in the same O rca package. Although the TDDFT method can accurately describe the equilibrium geometries of excited states and their energies, it cannot accurately determine the CI points due to the problem of the wrong dimensionality of the CI between ground and excited states at the TDDFT level ( Levine et al, 2006 ; Huix-Rotllant et al, 2016 ; Huix-Rotllant et al, 2020 ).…”

Section: Methodsmentioning

confidence: 99%

“…is the triples correction term to the inter-fragment interaction energy. The electronically excited states were also computed considering the SCS-PBE-QIDH XC functional (Casanova-Páez and Goerigk, 2021) built as the spin-component scaled version of Adamo's PBE-based double hybrid (Brémond et al, 2014) optimized for excited states, all of them implemented in the same Orca package. Although the TDDFT method can accurately describe the equilibrium geometries of excited states and their energies, it cannot accurately determine the CI points due to the problem of the wrong dimensionality of the CI between ground and excited states at the TDDFT level (Levine et al, 2006;Huix-Rotllant et al, 2016;Huix-Rotllant et al, 2020).…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Theoretical Study of Light-Induced Crosslinking Reaction Between Pyrimidine DNA Bases and Aromatic Amino Acids

Bende

Farcaș

Toşa

2022

Front. Bioeng. Biotechnol.

View full text Add to dashboard Cite

Low-lying electronic excited states and their relaxation pathways as well as energetics of the crosslinking reaction between uracil as a model system for pyrimidine-type building blocks of DNA and RNA and benzene as a model system for aromatic groups of tyrosine (Tyr) and phenylalanine (Phe) amino acids have been studied in the framework of density functional theory. The equilibrium geometries of the ground and electronic excited states as well as the crossing points between the potential energy surfaces of the uracil–benzene complex were computed. Based on these results, different relaxation pathways of the electronic excited states that lead to either back to the initial geometry configuration or the dimerization between the six-membered rings of the uracil–benzene complex have been identified, and the energetic conditions for their occurrence are discussed. It can be concluded that the DNA–protein crosslinking reaction can be induced by the external electromagnetic field via the dimerization reaction between the six-membered rings of the uracil–benzene pair at the electronic excited-state level of the complex. In the case of the uracil–phenol complex, the configuration of the cyclic adduct (dimerized) conformation is less likely to be formed.

show abstract

“…The inter-fragment interaction energy can be written as follows:

where

means the electronic preparation (or intra-fragment reference) energy and describes how much energy is necessary to bring the fragments into the electronic structure that is optimal for interaction,

, and

are the inter-fragment electrostatic and exchange contributions,

and

are the non-dispersive and dispersive parts of the correlation energy at the CCSD level, and

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Theoretical Study of Light-Induced Crosslinking Reaction Between Pyrimidine DNA Bases and Aromatic Amino Acids

Bende

Farcaș

Toşa

2022

Front. Bioeng. Biotechnol.

View full text Add to dashboard Cite

show abstract

“…Moreover, it should be pointed out that an effect of ~0.05 eV is rather large in relation to the "chemical accuracy" threshold often sought for calculated excitation energies, [90] which by some researchers is set at 1 kcal mol À 1 � 0.04 eV, [5,11] whereas others prefer 0.1 eV. [106] At the same time, the effect is small compared to the average errors that all density functionals, including accurate double hybrids ones, [90,[107][108][109] show for excitation energies. Thus, the effect is not likely to be the main source of error when such calculations are performed in a static fashion.…”

Section: Comparison Static and Dynamical Calculationsmentioning

confidence: 99%

Thermal Fluctuations in Conjugation and their Effect on Calculated Excitation Energies: A Case Study on the Astaxanthin Carotenoid

Wang¹,

Durbeej

2021

ChemPhotoChem

View full text Add to dashboard Cite

A popular approach to the calculation of molecular excitation energies is to consider only equilibrium geometries and neglect the effects of thermal motion. Although this static approach is sensible for molecules with distinct potential-energy minima, its adequacy relative to dynamical approaches appears not to have been thoroughly tested. Here, we report a case study investigating how thermal motion accounted for by molecular dynamics simulations influences the optically bright state of astaxanthin, a carotenoid of broad photobiological interest that features 13 conjugated double bonds. Employing several different density functional methods, it is shown that thermal fluctuations in the conjugation result in the Boltzmann-weighted average excitation energies for this state being shifted by up to 0.05 eV relative to those obtained from purely static calculations. Accordingly, it is concluded that the effects of thermal motion on excitation energies of conjugated systems can be quite large even for molecules with distinct potential-energy minima.

show abstract

“…Linear-response time-dependent DFT within the adiabatic approximation [48][49][50] (TD-DFT) has become the method of choice to treat excited-state problems. Recent advances [51][52][53] and detailed benchmark studies [54][55][56][57][58][59][60][61][62][63][64] on singlemolecule cases have shed light on the quality of TD-DFAs for the calculation of excitation energies. As recently summarised for readers unfamiliar with the field, lower rungs on the Jacob's Ladder of DFT 65 should be avoided due to the emergence of artificial ghost states and large red shifts in excitation energies.…”

Section: Introductionmentioning

confidence: 99%

“…52,58,62,66,76 Time-dependent DHDFAs 77 depend additionally on a nonlocal, perturbative electron-correlation component 78 that compensates for many of the systematic errors of hybrids. 47,51,54,55,57,58,66,79 In fact, our group recently developed RS-DHDFAs 52,53 that belong to some of the currently most robust TD-DFT methods for a variety of different local and long-range valence excitations in organic molecules. 52,53,[62][63][64] A slightly dif- ferent group of RS-DHDFAs have also proven to be very promising when used within the Tamm-Dancoff Approximation 80 (TDA-DFT).…”

Section: Introductionmentioning

confidence: 99%

Noncovalently bound excited-state dimers: a perspective on current time-dependent Density Functional Theory approaches applied to aromatic excimer models

Hancock

Goerigk

2022

Preprint

Self Cite

View full text Add to dashboard Cite

Excimers are supramolecular systems whose binding strength is influenced by many factors that are ongoing challenges for computational methods, such as charge transfer, exciton coupling, and London dispersion interactions. Treating the various intricacies of excimer binding at an adequate level is expected to be particularly challenging for time-dependent Density Functional Theory (TD- DFT) methods. In addition to well-known limitations for some TD-DFT methods in the description of charge transfer or exciton coupling, the inherent London dispersion problem from ground-state DFT translates to TD-DFT. While techniques to appropriately treat dispersion in DFT are well- developed for electronic ground states, these dispersion corrections remain largely untested for excited states. Herein, we aim to shed light on current TD-DFT methods, including some of the newest developments. The binding of four model excimers is studied across nine density functionals with and without the application of additive dispersion corrections against a wave function reference of SCS-CC2/CBS(3,4) quality, which approximates select CCSDR(3)/CBS data adequately. To our knowledge, this is the first study that presents single-reference wave function dissociation curves at the complete basis set level for the assessed model systems. It is also the first time range-separated double-hybrid density functionals are applied to excimers. In fact, those functionals turn out to be the most promising for the description of excimer binding followed by global double hybrids. Range-separated and global hybrid—particularly with large fractions of Fock exchange—are outperformed by double hybrids and yield worse dissociation energies and inter-molecular equilibrium distances. The deviation between assessed functional and reference increases with system size, most likely due to missing dispersion interactions. Additive dispersion corrections of the DFT-D3(BJ) and DFT-D4 types reduce the average errors for TD-DFT methods but do so inconsistently and therefore do not offer a black-box solution in their ground-state parametrised form. The lack of appropriate description of dispersion effects for TD-DFT methods is likely hindering the practical application of the herein identified more efficient methods. Dispersion corrections parametrised for excited states appear to be an important next step to improve the applicability of TD-DFT methods and we hope that our work assists with the future development of such corrections.

show abstract

Time-Dependent Long-Range-Corrected Double-Hybrid Density Functionals with Spin-Component and Spin-Opposite Scaling: A Comprehensive Analysis of Singlet–Singlet and Singlet–Triplet Excitation Energies

Cited by 73 publications

References 137 publications

Theoretical Study of Light-Induced Crosslinking Reaction Between Pyrimidine DNA Bases and Aromatic Amino Acids

Theoretical Study of Light-Induced Crosslinking Reaction Between Pyrimidine DNA Bases and Aromatic Amino Acids

Thermal Fluctuations in Conjugation and their Effect on Calculated Excitation Energies: A Case Study on the Astaxanthin Carotenoid

Noncovalently bound excited-state dimers: a perspective on current time-dependent Density Functional Theory approaches applied to aromatic excimer models

Contact Info

Product

Resources

About