Resonant two-photon ionization spectroscopy of jet-cooled PdSi

Martinez, Alonzo; Lindholm, Ned F.; Morse, Michael D.

doi:10.1063/1.3642602

Cited by 7 publications

(3 citation statements)

References 61 publications

(27 reference statements)

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“…From the previous theoretical calculations performed on neutral PdSi, consensus has been that the most likely ground state is the 1 S + state, 16,94 instead of the 3 P r state. 95 Recently, Martinez et al 66 also supported the spin singlet 1 S + state to be the PdSi ground state experimentally via resonant two-photon ionization spectroscopy. Starting from the 1 S + : 1s 2 2s 2 1p 4 1d 4 3s 2 2p 0 ground state, the candidates for the anion ground state are: a quartet state with configuration; 1s 2 2s 2 1p 4 1d 4 3r 1 2p 2 or a doublet state with configuration; 1s 2 2s 2 1p 4 1d 4 3s 2 2p 1 .…”

Section: Pdsimentioning

confidence: 94%

“…The electronic structures of transition metal silicide diatomics have received significant experimental attention over the years. CuSi, 61 AgSi, 62 AuSi 63 and PtSi 64 molecules have been studied using cavity ring down absorption spectroscopy, while RuSi, 65 PdSi, 66 PtSi 67 and NiSi 68 molecules have been probed via resonant two photon-ionization spectroscopic and dispersed fluorescence investigations. Laser-induced fluorescence experiments on RhSi 65 and the above mentioned experimental work on transition metal diatoms generally assign ground and excited states of the neutral diatomics by combining experimental and theoretical results.…”

Section: Introductionmentioning

confidence: 99%

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Probing the valence orbitals of transition metal–silicon diatomic anions: ZrSi, NbSi, MoSi, PdSi and WSi

Gunaratne

Berkdemir

Harmon

et al. 2013

Phys. Chem. Chem. Phys.

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Evolution of electronic properties and the nature of bonding of the 4d-transition metal silicides (ZrSi, NbSi, MoSi and PdSi) are discussed, revealing interesting trends in the transition metal-silicon interactions across the period. The electronic properties of select transition metal silicide diatomics have been determined by anion photoelectron imaging spectroscopy and theoretical methods. The electron binding energy spectra and photoelectron angular distributions obtained by 2.33 eV (532 nm) photons have revealed the distinct features of these diatomics. The theoretical calculations were performed at the density functional theory (DFT) level using the unrestricted B3LYP hybrid functional and at the ab initio unrestricted coupled cluster singles and doubles (triplets) (UCCSD(T)) methods to assign the ground electronic states of the neutral and anionic diatomics. The excited electronic states were calculated by the DFT (TD-DFT)/UB3LYP method. We have observed that the valence molecular orbital configuration of the ZrSi and NbSi anions are significantly different from that of the MoSi and PdSi anions. By combining our experimental and theoretical results, we report that the composition of the highest occupied molecular orbitals shift from a majority of transition metal s- and d-orbital contribution in ZrSi and NbSi, to mainly silicon p-orbital contribution for MoSi and PdSi. We expect these observed atomic scale transition metal-silicon interactions to be of increasing importance with the miniaturization of devices approaching the sub-nanometer size regime.

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Section: Pdsimentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

Probing the valence orbitals of transition metal–silicon diatomic anions: ZrSi, NbSi, MoSi, PdSi and WSi

Gunaratne

Berkdemir

Harmon

et al. 2013

Phys. Chem. Chem. Phys.

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“…In the present work, copper acetylide, CuCCH, was investigated using resonant two-photon ionization spectroscopy (R2PI). The instrument employed is identical to that used in many previous studies. − The CuCCH molecule is produced by focusing the third harmonic radiation from a Q-switched Nd:YAG laser (355 nm, 3–6 mJ/pulse, measured at the sample) onto a copper sample in the throat of a pulsed supersonic expansion of helium (60–120 psig backing pressure) that is seeded with a small percentage of acetylene. The copper sample is a disk that is rotated and translated to prevent the ablation laser from drilling a hole in the sample.…”

Section: Methodsmentioning

confidence: 99%

Electronic Spectroscopy and Electronic Structure of Copper Acetylide, CuCCH

Díaz-García

Morse

2013

J. Phys. Chem. A

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The optical spectrum of the linear CuCCH molecule has been investigated for the first time, using resonant two-photon ionization spectroscopy employing ArF (193 nm) or F2 (157 nm) excimer radiation for photoionization. Scans over the range 19 400-25 200 cm(-1) were conducted, leading to the observation of three electronic band systems. These are identified as the [20.2] ã1 ← X̃ (1)Σ(+), the [23.1] Ã (1)Σ(+) ← X̃ (1)Σ(+), and the [24.7] B̃ (1)Π ← X̃ (1)Σ(+) systems, although only the first two have been rotationally resolved. The ã1 state is tentatively assigned as having (3)Π1 symmetry, becoming optically accessible through spin-orbit interaction with the B̃ (1)Π state. Vibrational assignments have provided the frequency of the Cu-C stretching mode, ν3, in the ground and all three excited states, along with both bending modes, ν4 and ν5, in the Ã (1)Σ(+) and B̃ (1)Π states, and the Cu-C≡C bending mode, ν5, in the ground state. Comparisons are made to the known electronic states of CuF, CuCl, CuBr, and CuI, and it is argued that like these molecules, the CuCCH molecule is essentially ionic in both the ground and excited states, with the ground state correlating diabatically to Cu(+) (3d(10), (1)S) + CCH(-) (X̃ (1)Σ(+)) and the excited states correlating diabatically to Cu(+) (3d(9)4s(1), (1,3)D) + CCH(-) (X̃ (1)Σ(+)).

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Electronic spectroscopy and electronic structure of diatomic IrSi

Díaz-García

Vietz

Ruipérez

et al. 2013

The Journal of Chemical Physics

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The optical spectrum of diatomic IrSi has been investigated for the first time, with transitions observed in the range from 17,178 to 23,858 cm(-1) (582-419 nm). A rich spectrum has been recorded, consisting of 14 electronic band systems and a number of unclassified bands. Thirty-one bands have been investigated with rotational resolution, allowing the ground state to be identified as X(2)Δ5∕2 arising from the 1σ(2)1π(4)2σ(2)1δ(3)3σ(2) configuration. The ground X(2)Δ5∕2 state is characterized by ΔG1∕2 = 533 cm(-1) and r0 = 2.0899(1) Å for the more abundant isotopic form, (193)Ir(28)Si (57.8%). The measured excited electronic states have equilibrium bond lengths ranging from 2.17 to 2.25 Å and vibrational frequencies ranging from 365 to 452 cm(-1). Ab initio calculations were also carried out on the molecule using the complete active space self-consistent field and multistate complete active space second-order perturbation theory methods, with relativistic and spin-orbit effects included through the restricted active space state-interaction with spin-orbit coupling method. The calculated ground state agrees with experiment, and a large number of excited states lying within 20,000 cm(-1) of the ground state are reported.

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Resonant two-photon ionization spectroscopy of jet-cooled PdSi

Cited by 7 publications

References 61 publications

Probing the valence orbitals of transition metal–silicon diatomic anions: ZrSi, NbSi, MoSi, PdSi and WSi

Probing the valence orbitals of transition metal–silicon diatomic anions: ZrSi, NbSi, MoSi, PdSi and WSi

Electronic Spectroscopy and Electronic Structure of Copper Acetylide, CuCCH

Electronic spectroscopy and electronic structure of diatomic IrSi

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