Analysis of multi-configuration density functional theory methods: theory and model application to bond-breaking

Kurzweil, Yair; Lawler, Keith V.; Head‐Gordon, Martin

doi:10.1080/00268970903160597

Cited by 29 publications

(33 citation statements)

References 44 publications

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“…47,48 While WFT-in-DFT methods aim at a multiscale description of large systems, MC-PDFT as well as sr-DFT-lr-WFT methods pursue similar objectives as DFT/MRCI. In the beginning, the combinations of generalized valence bond theory in perfect-pairing approximation 57,58 or minimal CASSCF or CASCI with DFT [59][60][61][62][63][64] were mostly thought to provide a proper description of bond dissociation processes in the electronic ground state. Later approaches used larger active spaces and additionally addressed electronically excited states [65][66][67][68][69] or strived for correcting the long-range behavior of TDDFT in describing CT states.…”

Section: Alternative Approachesmentioning

confidence: 99%

The DFT/MRCI method

Marian

Heil

Kleinschmidt

2018

WIREs Comput Mol Sci

142

154

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In the past two decades, the combined density functional theory and multireference configuration interaction (DFT/MRCI) method has developed from a powerful approach for computing spectral properties of singlet and triplet excited states of large molecules into a more general multireference method applicable to states of all spin multiplicities. In its original formulation, it shows great efficiency in the evaluation of singlet and triplet excited states which mainly originate from local one-electron transitions. Moreover, DFT/MRCI is one of the few methods applicable to large systems that yields the correct ordering of states in extended π-systems where double excitations play a significant role. A recently redesigned DFT/MRCI Hamiltonian extends the application range of the method to bichromophores such as hydrogen-bonded or π-stacked dimers and loosely coupled donor-acceptor systems. In conjunction with a restricted-open shell Kohn-Sham optimization of the molecular orbitals, even electronically excited doublet and quartet states can be addressed. After a short outline of the general ideas behind this semi-empirical method and a brief review of alternative approaches combining density functional and multireference wavefunction theory, formulae for the DFT/MRCI Hamiltonian matrix elements are presented and the adjustments of the two-electron contributions are discussed. The performance of the DFT/MRCI variants on excitation energies of organic molecules and transition metal compounds against experimental or ab initio reference data is analyzed and case studies are presented which show the strengths and limitations of the method. Finally, an overview over the properties available from DFT/MRCI wavefunctions and further developments is given.ABBREVIATIONS: ACRXTN, 3-(9,9-dimethylacridin-10[9H]-yl)-9H-xanthen-9-one; AO, atomic orbital; CASSCF, Complete active space self-consistent field; CASPT2, Complete active space second-order perturbation theory; CCSD(T), Coupled-cluster with singles and doubles and perturbative treatment of triples; CC2, Coupled-cluster with approximate treatment of doubles; CD, Circular dichroism; CI, Configuration interaction; CIPSI, configuration interaction by perturbation with multiconfigurational zeroth-order wave functions selected by iterative

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Section: Alternative Approachesmentioning

confidence: 99%

The DFT/MRCI method

Marian

Heil

Kleinschmidt

2018

WIREs Comput Mol Sci

142

154

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“…The development of a density functional theory including nondynamic (or "strong") electron correlation -which Becke designated as the "last frontier" in DFT [97] -has been pursued by many groups following different approaches. Among these approaches, we may cite the use of restricted open-shell ground-state representations [98], configuration ensembles with fractional occupations [91,[99][100][101], configuration interaction [102,103], multiconfigurational DFT [104], hybrid multiconfiguration/(TD)DFT [105,106], and spin-unrestricted broken-symmetry (UBS) [107] approaches. Unfortunately, analytical energy gradients are not available for most of these methods, which rules out their use in surface hopping dynamics.…”

Section: Critical Appraisalmentioning

confidence: 99%

Surface Hopping Dynamics with DFT Excited States

Barbatti

Crespo‐Otero

2014

Topics in Current Chemistry

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Nonadiabatic dynamics simulation of electronically-excited states has been a research area of fundamental importance, providing support for spectroscopy, explaining photoinduced processes, and predicting new phenomena in a variety of specialties, from basic physical-chemistry, through molecular biology, to materials engineering. The demands in the field, however, are quickly growing, and the development of surface hopping based on density functional theory (SH/DFT) has been a major advance in the field. In this contribution, the surface hopping approach, the methods for computation of excited states based on DFT, the connection between these methodologies, and their diverse implementations are reviewed. The shortcomings of the methods are critically addressed and a number of case studies from diverse fields are surveyed.

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“…The key‐idea of Dieter Cremer's CAS‐DFT approach was to treat the exchange part exactly at the CAS‐SCF level, while including dynamic correlation via a DFT correlation functional, as originally suggested by Miehlich, Stoll, and Savin) and implemented for GVB‐LSD by Elfi Kraka . Dieter Cremer and Jüergen Gräfenstein developed a CAS‐DFT program that allows an economic treatment of static and dynamic correlation effects in molecules with multi‐reference character and that master the basic CAS‐DFT problems: It avoids a double‐counting of correlation effects (a key problem in multi‐reference DFT), uses a two‐body rather than a one‐body correlation functional, is size‐consistent and free of any self‐interaction errors, and adjusts the correlation part to a changing active space . This approach has inspired the multi‐reference DFT developer community over the past decade …”

Section: Post‐scf Methodsmentioning

confidence: 99%

Dieter Cremer's contribution to the field of theoretical chemistry

Kraka

Cremer²

2019

Int J of Quantum Chemistry

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This legacy article reviews the contributions of Dieter Cremer (1944‐2017) to the field of theoretical chemistry, highlighting his major accomplishments in method development and applied quantum chemistry, which has led to many advances in the field. His work reflects an extraordinary breadth and deep understanding of theory, which is needed to solve complex chemical problems. His passion for science has inspired many colleagues in the past and will do so in the future.

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Analysis of multi-configuration density functional theory methods: theory and model application to bond-breaking

Cited by 29 publications

References 44 publications

The DFT/MRCI method

The DFT/MRCI method

Surface Hopping Dynamics with DFT Excited States

Dieter Cremer's contribution to the field of theoretical chemistry

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