<i>Ab initio</i> simulation of the vibrationally resolved photoelectron spectrum of Si3−

García‐Fernández, Pablo; Boggs, James E.; Stanton, John F.

doi:10.1063/1.2472329

Cited by 7 publications

(7 citation statements)

References 25 publications

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“…[14][15][16][17][18][19][20][21][22] For smaller anionic and cationic clusters, the combination of experiments with high level theory makes it possible to determine the structures of these clusters. [23][24][25] For medium-sized clusters, changes in the structural motif were suggested. Recently, we used infrared multiple photon dissociation (IR-MPD) to obtain vibrational spectra of cationic silicon clusters with 6 to 21 atoms.…”

Section: Introductionmentioning

confidence: 99%

Gas-phase structures of neutral silicon clusters

Haertelt

Lyon

Claes

et al. 2012

The Journal of Chemical Physics

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Vibrational spectra of neutral silicon clusters Si(n), in the size range of n = 6-10 and for n = 15, have been measured in the gas phase by two fundamentally different IR spectroscopic methods. Silicon clusters composed of 8, 9, and 15 atoms have been studied by IR multiple photon dissociation spectroscopy of a cluster-xenon complex, while clusters containing 6, 7, 9, and 10 atoms have been studied by a tunable IR-UV two-color ionization scheme. Comparison of both methods is possible for the Si(9) cluster. By using density functional theory, an identification of the experimentally observed neutral cluster structures is possible, and the effect of charge on the structure of neutrals and cations, which have been previously studied via IR multiple photon dissociation, can be investigated. Whereas the structures of small clusters are based on bipyramidal motifs, a trigonal prism as central unit is found in larger clusters. Bond weakening due to the loss of an electron leads to a major structural change between neutral and cationic Si(8).

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Section: Introductionmentioning

confidence: 99%

Gas-phase structures of neutral silicon clusters

Haertelt

Lyon

Claes

et al. 2012

The Journal of Chemical Physics

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“…2 in Ref. 24). Unlike the quite simple triplet manifold, vibronic interactions are both numerous and complicated in the singlet spectrum, and their study will be addressed in a forthcoming publication.…”

Section: Results and Assignmentmentioning

confidence: 99%

“…10) by Garcia-Fernadez et al confirmed that the major contribution to the X-band is from the 3 A 2 electronic state. 24 In light of the substantial effort to understand the electronic structure of the silicon trimer, it is surprising that no gas-phase excitation spectrum has been reported for either isomer. In this article, we focus on the jet-cooled gas-phase spectrum of Si 3 in the 555-480 nm region, probed by resonant mass-selected two-color two-photon ionization (R2C2PI) and laser-induced fluorescence (LIF)/dispersed fluorescence (DF) spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

The electronic spectrum of Si3 I: Triplet D3h system

Reilly

Kokkin

Zhuang

et al. 2012

The Journal of Chemical Physics

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We report the measurement of a jet-cooled electronic spectrum of the silicon trimer. Si 3 was produced in a pulsed discharge of silane in argon, and the excitation spectrum examined in the 18 000-20 800 cm −1 region. A combination of resonant two-color two-photon ionization (R2C2PI) time-offlight mass spectroscopy, laser-induced fluorescence/dispersed fluorescence, and equation-of-motion coupled-cluster calculations have been used to establish that the observed spectrum is dominated by the 1 3 A 1 -ã 3 A 2 transition of the D 3h isomer. The spectrum has an origin transition at 18 600 ± 4 cm −1 and a short progression in the symmetric stretch with a frequency of ∼445 cm −1 , in good agreement with a predicted vertical transition energy of 2.34 eV for excitation to the 1 3 A 1 state, which has a calculated symmetric stretching frequency of 480 cm −1 . In addition, a ∼505 cmground state vibrational frequency determined from sequence bands and dispersed fluorescence is in agreement with an earlier zero-electron kinetic energy study of the lowest D 3h state and with theory. A weaker, overlapping band system with a ∼360 cm −1 progression, observed in the same mass channel (m/z = 84) by R2C2PI but under different discharge conditions, is thought to be due to transitions from the (more complicated) singlet C 2v ground state ( 1 A 1 ) state of Si 3 . Evidence of emission to this latter state in the triplet dispersed fluorescence spectra suggests extensive mixing in the excited triplet and singlet manifolds. Prospects for further spectroscopic characterization of the singlet system and direct measurement of the energy separation between the lowest singlet and triplet states are discussed.

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“…While C 3 has a singlet linear structure (X 1

Σ_{normalg}^{+}

) which is located at 1.91 eV (16930 cm −1 ) below the triplet linear a 3 Π u state, Si 3 is strongly bent with two close‐lying low‐spin 1 A 1 ( C 2v ) and high‐spin 3

{normalA}_{2}^{'}

( D 3h ) states. Previous extensive quantum chemical computations pointed out that the singlet C 2v structure is the lowest‐lying state of Si 3 , but the corresponding singlet–triplet gap turns out to be small, calculated in the range of 4–15 kJ/mol depending on the methods used …”

Section: Introductionmentioning

confidence: 99%

“…This triatomic species was produced in the 1980s in a number of mass spectrometry experiments using, among others, photofragmentation technique, and laser vaporization followed by a free jet expansion technique . Its electronic structure and spectroscopic parameters were subsequently the subject of several experimental, and theoretical studies . Thermochemical parameters including the total atomization energy (TAE), heat of formation, ionization energy, and electron affinity of Si 3 were also determined …”

Section: Introductionmentioning

confidence: 99%

Bonding and singlet–triplet gap of silicon trimer: Effects of protonation and attachment of alkali metal cations

et al. 2015

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We revisit the singlet-triplet energy gap (ΔE(ST)) of silicon trimer and evaluate the gaps of its derivatives by attachment of a cation (H(+), Li(+), Na(+), and K(+)) using the wavefunction-based methods including the composite G4, coupled-cluster theory CCSD(T)/CBS, CCSDT and CCSDTQ, and CASSCF/CASPT2 (for Si3) computations. Both (1)A1 and (3)A2' states of Si3 are determined to be degenerate. An intersystem crossing between both states appears to be possible at a point having an apex bond angle of around α = 68 ± 2° which is 16 ± 4 kJ/mol above the ground state. The proton, Li(+) and Na(+) cations tend to favor the low-spin state, whereas the K(+) cation favors the high-spin state. However, they do not modify significantly the ΔE(ST). The proton affinity of silicon trimer is determined as PA(Si3) = 830 ± 4 kJ/mol at 298 K. The metal cation affinities are also predicted to be LiCA(Si3) = 108 ± 8 kJ/mol, NaCA(Si3) = 79 ± 8 kJ/mol and KCA(Si3) = 44 ± 8 kJ/mol. The chemical bonding is probed using the electron localization function, and ring current analyses show that the singlet three-membered ring Si3 is, at most, nonaromatic. Attachment of the proton and Li(+) cation renders it anti-aromatic.

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Ab initio simulation of the vibrationally resolved photoelectron spectrum of Si3−

Cited by 7 publications

References 25 publications

Gas-phase structures of neutral silicon clusters

Gas-phase structures of neutral silicon clusters

The electronic spectrum of Si3 I: Triplet D3h system

Bonding and singlet–triplet gap of silicon trimer: Effects of protonation and attachment of alkali metal cations

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