Tailored coupled cluster singles and doubles method applied to calculations on molecular structure and harmonic vibrational frequencies of ozone

Hino, Osamu; Kinoshita, Tomoko; Chan, Garnet Kin‐Lic; Bartlett, Rodney J.

doi:10.1063/1.2180775

Cited by 91 publications

(57 citation statements)

References 63 publications

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“…The average error is only 0.38 cm −1 (calculations with atomic masses) or 0.20 cm −1 (calculations with nuclear masses) that represents a drastic improvement with respect to other recent ab initio calculations. 142,143 For dark vibrational states and low resolution Raman bands our ab initio predictions are in average within the margins of experimental errors.…”

Section: Discussionsupporting

confidence: 61%

New analytical model for the ozone electronic ground state potential surface and accurate ab initio vibrational predictions at high energy range

Tyuterev

Kochanov

Tashkun

et al. 2013

The Journal of Chemical Physics

105

137

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An accurate description of the complicated shape of the potential energy surface (PES) and that of the highly excited vibration states is of crucial importance for various unsolved issues in the spectroscopy and dynamics of ozone and remains a challenge for the theory. In this work a new analytical representation is proposed for the PES of the ground electronic state of the ozone molecule in the range covering the main potential well and the transition state towards the dissociation. This model accounts for particular features specific to the ozone PES for large variations of nuclear displacements along the minimum energy path. The impact of the shape of the PES near the transition state (existence of the "reef structure") on vibration energy levels was studied for the first time. The major purpose of this work was to provide accurate theoretical predictions for ozone vibrational band centres at the energy range near the dissociation threshold, which would be helpful for understanding the very complicated high-resolution spectra and its analyses currently in progress. Extended ab initio electronic structure calculations were carried out enabling the determination of the parameters of a minimum energy path PES model resulting in a new set of theoretical vibrational levels of ozone. A comparison with recent high-resolution spectroscopic data on the vibrational levels gives the root-mean-square deviations below 1 cm(-1) for ozone band centres up to 90% of the dissociation energy. New ab initio vibrational predictions represent a significant improvement with respect to all previously available calculations.

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Section: Discussionsupporting

confidence: 61%

New analytical model for the ozone electronic ground state potential surface and accurate ab initio vibrational predictions at high energy range

Tyuterev

Kochanov

Tashkun

et al. 2013

The Journal of Chemical Physics

105

137

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“…[11][12][13] We should mention that there are many attempts in the literature to describe static correlation using some variant of CC. 14,15 Some examples are multireference CC which includes several different approaches, [16][17][18][19][20][21][22][23] variational CC methods which, however, are only applicable to small systems, 24,25 or the CC valence bond (CCVB) method, and its variant CCVB-SD, that improve upon the restricted CCSD description for strongly correlated systems. 26,27 Bytautas et al have shown that the low seniority sectors of Hilbert space are most important for the description of static correlation.…”

Section: Introductionmentioning

confidence: 99%

Seniority zero pair coupled cluster doubles theory

Stein

Henderson

Scuseria

2014

The Journal of Chemical Physics

191

234

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Coupled cluster theory with single and double excitations accurately describes weak electron correlation but is known to fail in cases of strong static correlation. Fascinatingly, however, pair coupled cluster doubles (p-CCD), a simplified version of the theory limited to pair excitations that preserve the seniority of the reference determinant (i.e., the number of unpaired electrons), has mean field computational cost and is an excellent approximation to the full configuration interaction (FCI) of the paired space provided that the orbital basis defining the pairing scheme is adequately optimized. In previous work, we have shown that optimization of the pairing scheme in the seniority zero FCI leads to a very accurate description of static correlation. The same conclusion extends to p-CCD if the orbitals are optimized to make the p-CCD energy stationary. We here demonstrate these results with numerous examples. We also explore the contributions of different seniority sectors to the coupled cluster doubles (CCD) correlation energy using different orbital bases. We consider both Hartree-Fock and Brueckner orbitals, and the role of orbital localization. We show how one can pair the orbitals so that the role of the Brueckner orbitals at the CCD level is retained at the p-CCD level. Moreover, we explore ways of extending CCD to accurately describe strongly correlated systems.

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“…A set of closely related approaches tries to catch the multireference character by external corrections, such as the reduced multireference coupled‐cluster (RMR‐CC) scheme,53,54 or by implying restrictions on the cluster amplitudes, such as the tailored coupled‐cluster (TCC) method 55,56. The RMR‐CC scheme makes use of the fact that the CCSD amplitude equations couple to quadruple excitations at most.…”

Section: Ansätze For Mrcc Wavefunctionsmentioning

confidence: 99%

State‐specific multireference coupled‐cluster theory

Köhn

Hanauer

Mück

et al. 2012

WIREs Comput Mol Sci

128

106

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The multireference problem is considered one of the great challenges in coupled‐cluster (CC) theory. Most recent developments are based on state‐specific approaches, which focus on a single state and avoid some of the numerical problems of more general approaches. We review various state‐of‐the‐art methods, including Mukherjee's state‐specific multireference coupled‐cluster (Mk‐MRCC) theory, multireference Brillouin–Wigner coupled‐cluster (MR‐BWCC) theory, the MRexpT method, and internally contracted multireference coupled‐cluster (ic‐MRCC) theory. Related methods such as extended single‐reference schemes [e.g., the complete active space coupled‐cluster (CASCC) theory] and canonical transformation (CT) theory are covered as well. The comparison is done on the basis of formal arguments, implementation issues, and numerical results. Although a final and generally accepted multireference CC theory is still lacking, it is emphasized that recent developments render the new MRCC schemes useful tools for solving chemical problems. © 2012 John Wiley & Sons, Ltd. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods

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Tailored coupled cluster singles and doubles method applied to calculations on molecular structure and harmonic vibrational frequencies of ozone

Cited by 91 publications

References 63 publications

New analytical model for the ozone electronic ground state potential surface and accurate ab initio vibrational predictions at high energy range

New analytical model for the ozone electronic ground state potential surface and accurate ab initio vibrational predictions at high energy range

Seniority zero pair coupled cluster doubles theory

State‐specific multireference coupled‐cluster theory

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