Laser vaporization generation of B 14NH, B 15NH, B 14ND, B 16O, and B 17O: Electron-spin-resonance investigation in neon matrices under ultracold trapping conditions

Knight, Lon B.; Herlong, John O.; Kirk, Thomas J.; Arrington, Caleb A.

doi:10.1063/1.462703

Cited by 40 publications

(27 citation statements)

References 33 publications

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“…Knight et al 38,20 used this method to estimate the atomic orbital character of the singly occupied molecular orbital of BO, AlO, GaO, and InO. These FACM predictions reproduce the bonding trend that is shown in Table II for this series of metal oxide radicals: going from BO to InO the oxygen 2p character increases and the metal ns valence character decreases.…”

Section: A Electronic Structure Calculationsmentioning

confidence: 94%

An evaluation of the density functional approach in the zero order regular approximation for relativistic effects: Magnetic interactions in small metal compounds

Belanzoni

Lenthe²,

Baerends³

2001

The Journal of Chemical Physics

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The performance of the density functional approach in the relativistic zero order regular approximation for the evaluation of electron spin resonance ͑ESR͒ parameters in small metal compounds has been evaluated critically by comparison with experimental data and available theoretical results for 22 linear molecules, characterized by a 2 ⌺ electronic ground state. For most of the molecules studied the calculated magnetic parameters are in good (A tensors͒ or reasonable (g tensors͒ agreement with experiment. Effects of spin-orbit coupling and spin polarization on the calculated hyperfine interaction are investigated. These two effects can only be evaluated separately, since the present method does not allow us to take spin-polarization effects into account in spin-orbit coupled density functional calculations. However, while spin-polarization effects are important for all the molecules investigated, spin-orbit effects are non-negligible only for the molecules containing heavier metal atoms. The ESR parameters, evaluated using different ''standard'' exchange-correlation potentials, have only shown little dependence on the specific functional. Direct relativistic contributions to the hyperfine parameters are often large, especially for the heavier metals, but also ''secondary'' contributions to the ligand hyperfine parameters can be large if the ligand is bound to a heavy element.

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Section: A Electronic Structure Calculationsmentioning

confidence: 94%

An evaluation of the density functional approach in the zero order regular approximation for relativistic effects: Magnetic interactions in small metal compounds

Belanzoni

Lenthe²,

Baerends³

2001

The Journal of Chemical Physics

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“…Values for the dipolar HFCCs at 5 bohr have been collected in Table 8 For GaO and its Rg complexes, HFCCs have been obtained only for Rg 12 and Rg 14 systems. They are displayed in Table 9 and will in the following section be used for comparison with the AlO and BO results.…”

Section: Resultsmentioning

confidence: 99%

“…A difference of about 20 MHz applied to the calculated gasphase value of 1466 MHz predicts an "experimental" gas-phase value of about 1445 MHz. The "experimental" A iso (Ga) in an Ar matrix is then estimated to be about 1890 MHz, arrived at by deducting 20 MHz from the value calculated for Ar 12 Hyperfine coupling constants can be related to the neutral and ionic structures I-III of the XO radicals, I being X(s 2 p 1 ) + O(s 2 p 4 ), II being X + (s 2 ) + O -(s 2 p 5 ), and III being X 2+ (s) + O 2-(s 2 p 6 ). Looking at the atomic open shells, A iso (X) is then due mainly to the doubly ionized structure III, which has an open-shell s orbital on X, and A dip (X) to the neutral structure I with an open p-shell on X.…”

Section: Discussionmentioning

confidence: 99%

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Rare Gas Effects on Hyperfine Coupling Constants of BO, AlO, and GaO

Grein

2005

J. Phys. Chem. A

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Using density functional theory methods and large basis sets, we calculated hyperfine coupling constants (HFCCs) for the (11)B, (17)O, (27)Al, and (69)Ga nuclei of the radicals BO, AlO, and GaO (XO), embedded in 2-14 rare gas (Rg) Ne and Ar atoms. Kr atoms were included for AlO. The distance of the Rg atoms from XO was varied from 4 to 12 bohr. Matrix effects cause A(iso)(X) to increase, accompanied by decreases in A(dip)(X) and A(dip)(O), while A(iso)(O) remains close to zero. Changes are largest for AlO, slightly smaller for GaO, and very small for BO, in line with the molecular polarizabilities. Observed changes of A(iso)(X) and A(dip)(X) for BO in Ne matrixes and for AlO in Ne, Ar, and Kr matrixes are reproduced in complexes with 12 Rg atoms at distances of 5-6 bohr or 14 Rg atoms at distances of 6-7 bohr. For GaO, experimental data are available only in Ne matrixes. Theoretical results obtained for HFCCs of (17)O could not be verified due to insufficient experimental information. Estimates of HFCCs in matrixes not yet experimentally studied and for GaO in the gas phase have been made. Due to the interaction with rare gas atoms, p-spin density on the X and O atoms of XO is converted into s-spin density on X, thereby causing an increase (in magnitude) of A(iso)(X), accompanied by decreases in A(dip) of X and O. The higher polarizability of XO along the bond axis is reflected in complexes that have axial Rg atoms showing larger changes in HFCCs than comparable complexes without axial Rg atoms.

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“…In 1992, the HNB was first observed by Knight et al [1] in their matrix electron spin resonance spectroscopy experiment. In 1995, Andrews and coworkers [2] reported the infrared spectroscopy experiment of HNB.…”

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confidence: 92%

CASPT2 study on low‐lying states of HBN and HNB radicals

Cheng

Gong

et al. 2010

Int J of Quantum Chemistry

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ABSTRACT:In this study, some low-lying states of the HBN and HNB radicals have been studied using multiconfiguration second-order perturbation theory. The geometries of all stationary points along the potential energy surfaces (PESs) were optimized at the CASPT2/cc-pVQZ level. The ground and the first excited states of HBN were predicted to be X 2 ⌸ and A 2 ⌺ ϩ states, respectively. It was predicted that the ground state of HNB is X 2 ⌺ ϩ state. The A 2 ⌸ state of HNB has unique imaginary frequency, which was different from the previously published results. A bending local minimum M1 was found for the first time along the 1 2 AЉ PES, and the A 2 ⌸ state of HNB should be the transition state of the isomerization reactions for M1 7 M1. The CASPT2/ANO potential energy curves (PECs) of isomerization reactions for HBN 7 HNB were calculated as a function of HBN bond angle. By comparing the CASPT2 and CASSCF calculated results, we concluded that the influence of the dynamic electron correlation on HBN 7 HNB system is not large.

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Laser vaporization generation of B 14NH, B 15NH, B 14ND, B 16O, and B 17O: Electron-spin-resonance investigation in neon matrices under ultracold trapping conditions

Abstract: An investigation of collisional processes in a Dicke narrowed transition of water vapor in the 7.8 μ m spectral region by frequency down-chirped quantum cascade laser spectroscopy

Cited by 40 publications

References 33 publications

An evaluation of the density functional approach in the zero order regular approximation for relativistic effects: Magnetic interactions in small metal compounds

An evaluation of the density functional approach in the zero order regular approximation for relativistic effects: Magnetic interactions in small metal compounds

Rare Gas Effects on Hyperfine Coupling Constants of BO, AlO, and GaO

CASPT2 study on low‐lying states of HBN and HNB radicals

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