Energy decomposition analysis based on broken symmetry unrestricted density functional theory

The interplay between noncovalent interactions involving metal complexes may lead to the formation of aggregates (i.e., ground state dimers, trimers, n-mers, etc.), and this is often linked to dramatic changes in their physical and chemical properties as compared to the original properties of the isolated units. Dimers and trimers can also be formed in the excited state potential energy surfaces, i.e., excimers. Excimers are short-lived but are also often characterized by different optical properties from those of the isolated units. Understanding the nature of noncovalent interactions and the presence or not of cooperativity effects in both aggregates and excimers is thus extremely important to rationalize these variations. In this study, we present computational investigations on isoquinolinyl pyrazolate Pt(II) complexes. Our results highlight that cooperativity effects between noncovalent interactions, which are modulated by sterically demanding substituents and metallophilic Pt•••Pt interactions, are present only on certain investigated excimers. We use density functional theory (DFT) calculations to examine the cooperativity effects and the changes in the photophysical properties. Different descriptors of cooperativity effects between noncovalent interactions, including the synergetic, genuine nonadditive, and total interaction energies, were evaluated for a series of Pt(II) aggregates and excimers. In addition, energy decomposition analysis (EDA) calculations were performed to rationalize the origins of the cooperative effects. The cooperative effects in trimer excimers (in their lowest triplet excited state, i.e., T 1 ) led to shortened Pt••• Pt contacts as compared to the trimer aggregates. Furthermore, this synergy between noncovalent interactions is ultimately responsible for the formation of the excimers and the striking changes in the measured photophysical properties. More in detail, we report a change in the character of the lowest-lying triplet excited state when going from dimer excimers (i.e., of mixed triplet ligandcentered and triplet metal-to-ligand charge transfer ( 3 LC/ 3 MLCT) character) to trimer excimers (i.e., of triplet metal−metal-toligand charge transfer ( 3 MMLCT) character). The EDA reveals that the total interaction energy on trimer excimers is subtly controlled by the electrostatic and dispersion terms.

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“…were performed based on the generalized Kohn-Sham (GKS) scheme, i.e., GKS-EDA, as implemented in the Turbomole package. 67,68…”

Section: Scheme 1 a Representative Cooperativity Effect Between Non-covalent Interactions Reportedmentioning

confidence: 99%

Formation of Excimers in Isoquinolinyl Pyrazolate Pt(II) Complexes: Role of Cooperativity Effects

et al. 2020

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“…Recently, a new extension of GKS-EDA, named GKS-EDA(BS), 33 was presented for intermolecular interactions in open shell singlet (OSS) states, which are challenging for most of EDA methods due to the multi-reference character. These EDA methods are capable of handling various chemical problems, which were comprehensively reviewed in a recently published article.…”

Section: Introductionmentioning

confidence: 99%

“…EDA-PCM was developed for intermolecular interactions in the solvated environments. GKS-EDA is an improved version of LMO-EDA, overcoming some shortcomings when KS orbitals are applied.Recently, a new extension of GKS-EDA, named GKS-EDA(BS), 33 was presented for intermolecular interactions in open shell singlet (OSS) states, which are challenging for most of EDA methods due to the multi-reference character. These EDA methods are capable of handling various chemical problems, which were comprehensively reviewed in a recently published article.…”

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confidence: 99%

XEDA, a fast and multipurpose energy decomposition analysis program

et al. 2021

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A fast and multipurpose energy decomposition analysis (EDA) program, called XEDA, is introduced for quantitative analysis of intermolecular interactions. This program contains a series of variational EDA methods, including LMO-EDA, GKS-EDA and their extensions, to analyze non-covalent interactions and strong chemical bonds in various environments. XEDA is highly efficient with a similar computational scaling of single point energy calculations. Its efficiency and universality are validated by a series of test examples including van der Waals interactions, hydrogen bonds, radical-radical interactions and strong covalent bonds. | INTRODUCTIONEnergy decomposition analysis (EDA) methods have been widely used for the quantitative analysis of intermolecular interactions based on quantum mechanical calculations. [1][2][3][4][5][6][7][8][9][10][11][12] They divide total interaction energies of molecular systems into several physically meaningful components to explore the physical origin of intermolecular interactions. Over the past decades, lots of EDA methods have been proposed, which can be classified into three groups, perturbation EDA methods, 4-8 variational EDA methods, 9-34 and real-space EDA methods. [35][36][37] In 2009, a variational EDA method, named localized molecular orbitals-based EDA (LMO-EDA) was proposed by one of the present authors and coworker. 22 LMO-EDA can be used for exploring different weak and strong interactions by using Hartree-Fock (HF) and Kohn-Sham (KS) orbitals. To consider various interactions in complex systems, following LMO-EDA, 22 energy decomposition analysis with polarizable continuum model (EDA-PCM), 24 generalized Kohn-Sham energy decomposition analysis (GKS-EDA), 25 and their extensions, have been proposed in the last decade. EDA-PCM was developed for intermolecular interactions in the solvated environments. GKS-EDA is an improved version of LMO-EDA, overcoming some shortcomings when KS orbitals are applied.Recently, a new extension of GKS-EDA, named GKS-EDA(BS), 33 was presented for intermolecular interactions in open shell singlet (OSS) states, which are challenging for most of EDA methods due to the multi-reference character. These EDA methods are capable of handling various chemical problems, which were comprehensively reviewed in a recently published article. 11 Currently, the EDA methods mentioned above are implemented in various quantum chemical programs. For example, KM-EDA, 13 RVS-EDA, 17,18 and LMO-EDA 22 are included in the released version of GAMESS program; 38 ETS-NOCV-EDA 21 is implemented in ADF; 39 ALMO-EDA 20 is provided by Q-Chem. 40 Local-EDA 27 is available in ORCA. 41 SAPT 4-8 is involved in Q-Chem, 40 PSI4, 42 MOLPRO, 43 CamCASP, 44 and SAPT2020. 45 Our developed EDA methods were implemented in a home-made version of GAMESS. 38 Most recently, the GKS-EDA method has been implemented in Turbomole, 46 and used for the study of interactions in isoquinolinyl pyrazolate Pt(II) complexes. 47 Recently, all our developed EDA methods were reimplemented as a novel pro...

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“…Such extensions have been achieved for the pair interaction (PI)-EDA, 31 the constrained space orbital variation (CSOV) approach, 32 and many other popular EDA schemes. [33][34][35][36][37] Besides DFT-based approaches, extensions of wavefunction theory (WFT)-based EDA schemes to open-shell systems have also been achieved, including the recently developed local energy decomposition (LED) analysis under the quasi-restricted 38 domain-based local pair natural orbital (DLPNO) framework 21 and the extension of absolutely localized molecular orbital (ALMO)-EDA to restricted openshell second-order Møller-Plesset perturbation theory (ROMP2) 39 by some of us. 40 In this paper, we present the recent development and applications of ALMO-EDA for studying radical-molecule interactions, i.e., the interactions between open-shell and closedshell species.…”

Section: Introductionmentioning

confidence: 99%

Probing radical–molecule interactions with a second generation energy decomposition analysis of DFT calculations using absolutely localized molecular orbitals

Mao

Levine

Loipersberger

et al. 2020

Phys. Chem. Chem. Phys.

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Energy decomposition analysis based on broken symmetry unrestricted density functional theory

Cited by 17 publications

References 110 publications

Formation of Excimers in Isoquinolinyl Pyrazolate Pt(II) Complexes: Role of Cooperativity Effects

Formation of Excimers in Isoquinolinyl Pyrazolate Pt(II) Complexes: Role of Cooperativity Effects

XEDA, a fast and multipurpose energy decomposition analysis program

Probing radical–molecule interactions with a second generation energy decomposition analysis of DFT calculations using absolutely localized molecular orbitals

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