Millimeter- and submillimeter-wave spectroscopy of platinum monocyanide, PtCN

Okabayashi, Emi Y.; Ohteki, Toshiaki; Furuya, Takashi; Tanimoto, Mitsutoshi

doi:10.1016/j.cplett.2010.04.037

Cited by 13 publications

(9 citation statements)

References 43 publications

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“…(21) is assumed using Eq. (19) 2 3/2 substate is not strongly affected by the 2 1/2 substate of PtCl but PtF is. However, it is unlikely that the energy separation, 2 1/2 − 2 3/2 , of PtF is several times larger than that of PtCl.…”

Section: E Parity-dependent Magnetic Hyperfine Constant H 3/2qmentioning

confidence: 87%

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Microwave spectroscopy of platinum monofluoride and platinum monochloride in the X 2Π3/2 states

Ohteki

Kurahara²,

Okabayashi³

et al. 2012

The Journal of Chemical Physics

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Platinum monofluoride (PtF) and platinum monochloride (PtCl) were detected in the gas phase using a source-modulated microwave spectrometer. The PtF and PtCl radicals were generated in a free space cell using the sputtering reaction from a platinum sheet placed on the inner surface of a stainless steel cathode through a dc glow discharge plasma of CF(4) and Cl(2), respectively, diluted with Ar. Rotational transitions were measured in the region between 150 and 313 GHz. Rotational, centrifugal distortion, and several fine- and hyperfine-structure constants were determined by a least-squares analysis. The observed fine-structure spectral patterns indicate that both PtF and PtCl radicals have the (2)Π(3/2) electronic ground states, while the related cyanide PtCN and hydride PtH radicals have the (2)Δ(5/2) electronic ground states.

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Section: E Parity-dependent Magnetic Hyperfine Constant H 3/2qmentioning

confidence: 87%

“…18 For other species, we recently revealed, by using rotational spectroscopy, that PtCN also has the 2 5/2 electronic ground state. 19 However, information on platinum monohalides is much more limited. Experimental evidence has been obtained for platinum monochloride (PtCl) through the matrix isolated infrared spectrum.…”

Section: Introductionmentioning

confidence: 99%

Microwave spectroscopy of platinum monofluoride and platinum monochloride in the X 2Π3/2 states

Ohteki

Kurahara²,

Okabayashi³

et al. 2012

The Journal of Chemical Physics

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“…A similar reaction has been employed in microwave studies of transition metal monosulfides, FeS [21] and NiS [22], as well as platinum compounds, PtO [12], PtCO [23], PtCN [24], PtF [25], and PtCl [25]. The transition frequencies of PtS in the ground state were predicted using the molecular constants determined from the Fourier transform microwave spectrum [16].…”

Section: Methodsmentioning

confidence: 99%

Millimeter- and submillimeter-wave spectra of platinum monosulfide (PtS) in the state

Ohteki¹,

Yamamoto²,

Kurahara³

et al. 2012

Journal of Molecular Spectroscopy

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“…The energies of the first excited state, relative to the ground state, are calculated to be 2.5 and 0.6 kcal mol ¹1 for PtCN and PtNC, respectively. On the other hand, in PdCN and PdNC, the ground state character remains 2 , with a slight mixing of 2 ¬ 1/2 . This is because there is a relatively large energy difference between the ground and first-excited states of PdCN and PdNC; thus, the order of the lowest-lying states does not change even after considering the spinorbit coupling effects.…”

mentioning

confidence: 99%

“…The energy levels of spinorbit-coupled states were calculated through a diagonalization of the spinorbit coupling matrix where the diagonal terms are replaced with the RCCSD(T) energy for the respective electronic states. Under the assumption of linear geometry for PtCN, PtNC, PdCN, and PdNC, two-dimensional potential energy surfaces were determined for spinorbit-uncoupled ( ¦ states, respectively, and the latter bond length is much closer to the experimental values, 1.90114 ¡ (r 0 ) and 1.89872 ¡ (r (2) m that is approximation to r e ), measured for the ground state of PtCN with ³ = 5/2.…”

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confidence: 99%

Spin–Orbit Coupling Effects on Low-lying Electronic States of PtCN/PtNC and PdCN/PdNC

et al. 2016

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It was demonstrated that spinorbit coupling changed the lowest-lying electronic states of PtCN and PtNC from 2 to 2 ¦ 5/2 by highly correlated electronic structure theory, considering relativistic effects. On the other hand, the electronic ground states of PdCN and PdNC remained 2 1/2 , even after considering spinorbit coupling effects.Keywords: Relativistic effect | Spectroscopic constants | Platinum compoundPlatinum is a transition-metal element in the fifth row of the periodic table where relativistic effect plays a significant role. Due to recent progresses in molecular theory, it has become feasible to quantitatively evaluate the spectroscopic constants of transition-metal compounds containing Pt by applying the stateof-the-art ab initio molecular orbital theory that can treat both relativistic and electron correlation effects appropriately. Nowadays theoretical calculations play an important role in understanding and predicting the spectroscopic constants of molecules in cooperation with experiments. For PtCN, the electronic ground state was predicted to be 2 by theoretical calculations, 1 but recently it has been reported that the angular momentum of the electronic ground state about the PtCN bond axis was ³ = 5/2, originating from 2 ¦, obtained by the measurement of millimeter and sub-millimeter wave spectra.2 Through a private communication with the experimental group, 2 we performed theoretical calculations for PtCN and PtNC and reported preliminary results that their ground states were predicted to be 2 ¦ 5/2 by considering spinorbit coupling effects.3 Very recently, the other group also reported similar results for PtCN and PdCN, by theoretical calculations including spinorbit coupling effects. 4 In this paper, we have reported a summary of our quantum chemical calculations for the low-lying electronic states of PtCN and PtNC, to identify the electronic ground state and to determine the equilibrium structures and vibrational frequencies, by the highly accurate electronic structure theory, considering scalar relativistic effects, spinorbit coupling effects, and electron correlation effects. It is noted that there is no report of the experimental observation for PtNC. We also performed a set of the same calculations for PdCN and PdNC for comparisons. As for PdCN, Okabayashi and co-workers performed similar experiments to determine the ground state term, equilibrium geometries, and the PdC vibrational frequency. 2 ¬, and 2 ¦ states, respectively. The energy was calculated for these three electronic states by the spin-restricted open-shell coupled cluster singles and doubles with a perturbational estimate of triple-excitations (RCCSD(T)). The relativistic effects were considered by the third-order DouglasKroll relativistic one-electron integrals, 6 with relativistic basis sets, Sapporo-DKH3-QZP. 7,8 The spinorbit coupling elements were also calculated for the 2 , 2 ¬, and 2 ¦ states of PtCN, PtNC, PdCN, and PdNC, as well as the ground state of Pt atom ( 3 D), using the BreitPauli Hamiltonian scheme, 9 by...

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Millimeter- and submillimeter-wave spectroscopy of platinum monocyanide, PtCN

Cited by 13 publications

References 43 publications

Microwave spectroscopy of platinum monofluoride and platinum monochloride in the X 2Π3/2 states

Microwave spectroscopy of platinum monofluoride and platinum monochloride in the X 2Π3/2 states

Millimeter- and submillimeter-wave spectra of platinum monosulfide (PtS) in the state

Spin–Orbit Coupling Effects on Low-lying Electronic States of PtCN/PtNC and PdCN/PdNC

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