Atomic‐orbital‐symmetry based σ‐, π‐, and δ‐decomposition analysis of bond orders

Сизова, О. В.; Skripnikov, L. V.; Sokolov, Alexander Yu.; Sizov, V. V.

doi:10.1002/qua.21978

Cited by 15 publications

(8 citation statements)

References 41 publications

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“…TaN has triple bond order (one σ-bond and two π bonds) provided mainly by d-electrons of Ta and pelectrons of N [76][77][78][79]. Unpaired electrons in 3 ∆ 1 state are non-bonding electrons localized on Ta.…”

Section: Resultsmentioning

confidence: 99%

TaN molecule as a candidate for the search for aT,P-violating nuclear magnetic quadrupole moment

et al. 2015

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It is demonstrated that the TaN molecule is the best candidate to search for T,P-violating nuclear magnetic quadrupole moment (MQM), it also looks promising to search for other T,P-odd effects. We report results of coupled-cluster calculations of T,P-odd effects in TaN produced by the Ta nucleus MQM, electron electric dipole moment (EDM), scalar−pseudoscalar nucleus−electron interactions, also of the molecule-axis hyperfine structure constant and dipole moment. Nuclear calculations of 181 Ta MQM are performed to express the T,P-odd effect in terms of the strength constants of T,P-odd nuclear forces, proton and neutron EDM, QCD parameter θ and quark chromo-EDM.

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Section: Resultsmentioning

confidence: 99%

TaN molecule as a candidate for the search for aT,P-violating nuclear magnetic quadrupole moment

et al. 2015

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“…WBI bond orders of 1 are typically only observed for nonpolarized σ-bonds, with substantially smaller values for polarized σ-bonds. 29 Because metal−ligand bonds are intrinsically polarized toward the ligand, metalligand WBI values between 0 and 1 are expected for M−L bonds with σ-donating ligands such as the phosphanido and phosphane donors under consideration. The increased WBI of the Ir−P bond for the phosphanido donor as compared to the phosphane donor reflects a stronger covalency and stronger Ir−P σ-bond.…”

Section: Resultsmentioning

confidence: 99%

Nucleophilicity and P–C Bond Formation Reactions of a Terminal Phosphanido Iridium Complex

et al. 2015

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The diiridium complex [{Ir(ABPN2)(CO)}2(μ-CO)] (1; [ABPN2](-) = [(allyl)B(Pz)2(CH2PPh2)](-)) reacts with diphenylphosphane affording [Ir(ABPN2)(CO)(H) (PPh2)] (2), the product of the oxidative addition of the P-H bond to the metal. DFT studies revealed a large contribution of the terminal phosphanido lone pair to the HOMO of 2, indicating nucleophilic character of this ligand, which is evidenced by reactions of 2 with typical electrophiles such as H(+), Me(+), and O2. Products from the reaction of 2 with methyl chloroacetate were found to be either [Ir(ABPN2)(CO)(H)(PPh2CH2CO2Me)][PF6] ([6]PF6) or [Ir(ABPN2)(CO)(Cl)(H)] (7) and the free phosphane (PPh2CH2CO2Me), both involving P-C bond formation, depending on the reaction conditions. New complexes having iridacyclophosphapentenone and iridacyclophosphapentanone moieties result from reactions of 2 with dimethyl acetylenedicarboxylate and dimethyl maleate, respectively, as a consequence of a further incorporation of the carbonyl ligand. In this line, the terminal alkyne methyl propiolate gave a mixture of a similar iridacyclophosphapentanone complex and [Ir(ABPN2){CH═C(CO2Me)-CO}{PPh2-CH═CH(CO2Me)}] (10), which bears the functionalized phosphane PPh2-CH═CH(CO2Me) and an iridacyclobutenone fragment. Related model reactions aimed to confirm mechanistic proposals are also studied.

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“…These are so-called "Atoms-In-Compounds" (AIC) properties or characteristics [19,54,55] (since not only measurable properties but also other effective Hamiltonian parameters can be considered here which are not always measurable ). In a very good approximation the AIC properties are localized on a heavy atom and do not depend on the bonding electronic density in contrast to some other types of properties [56][57][58][59]. A very important example of the AIC properties is the magnetic dipole hyperfine structure (HFS) constant.…”

Section: Theoretical Detailsmentioning

confidence: 99%

Combined 4-component and relativistic pseudopotential study of ThO for the electron electric dipole moment search

Skripnikov

2016

The Journal of Chemical Physics

127

136

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A precise theoretical study of the electronic structure of heavy atom diatomic molecules is of key importance to interpret the experiments in the search for violation of time-reversal (T) and spatial-parity (P) symmetries of fundamental interactions in terms of the electron electric dipole moment, eEDM, and dimensionless constant, k, characterizing the strength of the T,P-odd pseudoscalar-scalar electron-nucleus neutral current interaction. The ACME collaboration has recently improved limits on these quantities using a beam of ThO molecules in the electronic HΔ state [J. Baron et al., Science 343, 269 (2014)]. We apply the combined direct relativistic 4-component and two-step relativistic pseudopotential/restoration approaches to a benchmark calculation of the effective electric field, E, parameter of the T,P-odd pseudoscalar-scalar interaction, W, and hyperfine structure constant in Δ13 state of the ThO molecule. The first two parameters are required to interpret the experimental data in terms of the eEDM and k constant. We have investigated the electron correlation for all of the 98 electrons of ThO simultaneously up to the level of the coupled cluster with single, double, and noniterative triple amplitudes, CCSD(T), theory. Contributions from iterative triple and noniterative quadruple cluster amplitudes for the valence electrons have been also treated. The obtained values are E = 79.9 GV/cm, W = 113.1 kHz. The theoretical uncertainty of these values is estimated to be about two times smaller than that of our previous study [L. V. Skripnikov and A. V. Titov, J. Chem. Phys., 142, 024301 (2015)]. It was found that the correlation of the inner- and outer-core electrons contributes 9% to the effective electric field. The values of the molecule frame dipole moment of the Δ13 state and the HΔ→XΣ transition energy of ThO calculated within the same methods are in a very good agreement with the experiment.

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Atomic‐orbital‐symmetry based σ‐, π‐, and δ‐decomposition analysis of bond orders

Cited by 15 publications

References 41 publications

TaN molecule as a candidate for the search for aT,P-violating nuclear magnetic quadrupole moment

TaN molecule as a candidate for the search for aT,P-violating nuclear magnetic quadrupole moment

Nucleophilicity and P–C Bond Formation Reactions of a Terminal Phosphanido Iridium Complex

Combined 4-component and relativistic pseudopotential study of ThO for the electron electric dipole moment search

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