Localized molecular orbitals for excited states of polyenals, polyendials, and polyenones

Pitarch‐Ruiz, J.; Evangelisti, Stefano; Maynau, Daniel

doi:10.1002/qua.10766

Cited by 16 publications

(20 citation statements)

References 31 publications

(29 reference statements)

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“…The short-range part which can be treated with the multi-reference version of the method of increments and the long-range fluctuations which are determined by a charge screening and can be approximated by a random-phase approximation (RPA). Similar attempts using localised orbitals for a multi-reference correlation treatment are proposed by Evangelisti et al [129,130,[143][144][145].…”

Section: Methods Of Incrementsmentioning

confidence: 90%

The method of increments—a wavefunction-based ab initio correlation method for solids

2006

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An overview of wavefunction-based correlation methods generalised for the application to solids is presented. Those methods based on a preceding Hartree-Fock treatment explicitly calculate the many-body wavefunction in contrast to the density-functional theory which relies on the ground-state density of the system. This review focus on the so-called method of increments where the correlation energy of the solid is expanded in terms of localised orbitals or of a group of localised orbitals. The method of increments is applied to a great variety of materials, from covalent semiconductors to ionic insulators, from large band-gap materials like diamond to the half-metal -tin, from large molecules like fullerenes over polymers, graphite to three-dimensional solids. Rare-gas crystals where the binding is van der Waals like are treated as well as solid mercury, where the metallic binding is entirely due to correlation. Strongly correlated systems are examined and the correlation driven metal-insulator transition is described at an ab initio level.

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Section: Methods Of Incrementsmentioning

confidence: 90%

The method of increments—a wavefunction-based ab initio correlation method for solids

2006

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“…Another problem concerns the process to obtain the most relevant active MOs relative to the excitation process. If they are obtained through a single configurational variational calculation of the excited state, they will tend to localize unduly in the center of the molecule [26] : the excitation keeps the same extent when the size of the system increases, and the calculated excitation does not change, while it should decrease (as known from experiment). This is due to the holeparticle attraction.…”

Section: Introductionmentioning

confidence: 98%

Implementation of renormalized excitonic method at ab initio level

Zhang

Malrieu

et al. 2011

J Comput Chem

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The renormalized excitonic method [Hajj et al., Phys Rev B 2005, 72, 224412], in which the excited state of the whole system may be described as a linear combination of local excitations, has been implemented at ab initio level. Its performance is tested on the ionization potential and the energy gap between singlet ground state and lowest triplet for linear molecular hydrogen chains and more realistic systems, such as polyenes and polysilenes, using full configuration interaction (FCI) wave functions with a minimal basis set. The influence of different block sizes and the extent of interblock interactions are investigated. It has been demonstrated that satisfactory results can be obtained if the near degeneracies between the model space and the outer space are avoided and if interactions between the next-nearest neighbor blocks are considered. The method can be used with larger basis sets and other accurate enough ab initio evaluations (instead of FCI) of local excited states, from blocks, or from dimers or trimers of blocks. It provides a new possibility to accurately and economically describe the low-lying delocalized excited states of large systems, even inhomogeneous ones.

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“…Most of these methods face the difficulties by means of multireference ͑MR͒ approaches ͓e.g., multireference configuration interaction ͑CI͒ more or less corrected for sizeconsistency error effects [5][6][7][8][9][10][11] or multireference perturbation theory [12][13][14][15] ͔. The extension of the single-reference configurations interaction ͑SR-CI͒ to the MR case is conceptually straightforward.…”

Section: Introductionmentioning

confidence: 99%

Full configuration interaction calculation of BeH adiabatic states

Pitarch‐Ruiz

Sánchez‐Marín

Velasco

et al. 2008

The Journal of Chemical Physics

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An all-electron full configuration interaction ͑FCI͒ calculation of the adiabatic potential energy curves of some of the lower states of BeH molecule is presented. A moderately large ANO basis set of atomic natural orbitals ͑ANO͒ augmented with Rydberg functions has been used in order to describe the valence and Rydberg states and their interactions. The Rydberg set of ANOs has been placed on the Be at all bond distances. So, the basis set can be described as 4s3p2d1f / 3s2p1d͑Be/ H͒ +4s4p2d͑Be͒. The dipole moments of several states and transition dipole strengths from the ground state are also reported as a function of the R Be-H distance. The position and the number of states involved in several avoided crossings present in this system have been discussed. Spectroscopic parameters have been calculated from a number of the vibrational states that result from the adiabatic curves except for some states in which this would be completely nonsense, as it is the case for the very distorted curves of the 3s and 3p

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Localized molecular orbitals for excited states of polyenals, polyendials, and polyenones

Cited by 16 publications

References 31 publications

The method of increments—a wavefunction-based ab initio correlation method for solids

The method of increments—a wavefunction-based ab initio correlation method for solids

Implementation of renormalized excitonic method at ab initio level

Full configuration interaction calculation of BeH adiabatic states

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