Excitation of zinc(4s4p'P1) within the zinc-xenon van der Waals complex: effect of p-orbital alignment on the production of zinc (4s4p3Pj)

Wallace, Ingvar; Kaup, John G.; Breckenridge, W. H.

doi:10.1021/j100174a013

Cited by 52 publications

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“…An understanding of the matrix luminescence was facilitated by the large body of complementary data available on the interaction potentials of diatomic zinc atom/rare gas atom van der Waals species (Zn•RG). These species have been generated in supersonic expansions by Breckenridge and co-workers [13][14][15][16][17] and Umemoto et al 18 and their ''pair-potentials'' have been used in well established 19 theoretical models 20 to simulate metal atom spectroscopy in the solid rare gases. Spectral simulations based on pair-potentials has allowed identification of the pairs of the emission bands present in the solid rare gases as due to two distinct vibronic modes coupling in the excited state.…”

Section: Introductionmentioning

confidence: 99%

Quenching of excited P11 state atomic zinc by molecular nitrogen: A matrix-isolation spectroscopy/quantum chemical calculation study

Colmenares

McCaffrey

Novaro

2001

The Journal of Chemical Physics

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A concentration study is used to identify the optical absorption of zinc atoms isolated in solid nitrogen. Photoexcitation of the threefold-split, atomic 4p 1 P 1 singlet absorption band did not produce any emission from either the singlet or triplet states. Hartree-Fock ͑relativistic effective core potentials͒ plus variational and multireference perturbational configuration-interaction calculations are performed to analyze this very efficient quenching of excited state atomic zinc by molecular nitrogen. Of the two geometries considered in energy calculations of the approach of Zn( 1 P 1 ) to N 2 , the collinear exhibited a slightly greater stabilization than the perpendicular approach. However, the collinear is identified as of no significance in the excited state quenching due to the absence of low energy crossings with the ground state. In contrast, for the perpendicular approach a crossing between the repulsive ground 1 A 1 ( 1 S 0 ) state and the strongly attractive 1 B 2 ( 1 P 1 ) state occurs close to the energy minimum of the 1 B 2 state. The efficiency of crossing between these states is analyzed in the framework of one-dimensional Landau-Zener ͑LZ͒ theory. A hopping probability of 0.07 is obtained for a single crossing, considered important in a rapidly relaxing solid state system, such as present in a low temperature matrix. Crossings found between the repulsive 3 B 1 ( 3 P 1 ) and 3 A 1 ( 3 P 1 ) states with the strongly bound 1 B 2 ( 1 P 1 ) state are expected to play a role in gas phase Zn( 1 P 1 ) quenching leading to the production of Zn( 3 P J ) states. LZ calculations indicate a small hopping probability for these crossings, consistent with the small 1 P 1 → 3 P J quenching cross sections observed in the gas phase work.

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Section: Introductionmentioning

confidence: 99%

Quenching of excited P11 state atomic zinc by molecular nitrogen: A matrix-isolation spectroscopy/quantum chemical calculation study

Colmenares

McCaffrey

Novaro

2001

The Journal of Chemical Physics

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“…This reflects the difficulty of accurately calculating weak van der Waals interaction energies. Introduction Supersonic beam and laser spectroscopic methods have been extensively employed to observe transitions between bound vibrational levels of weakly bound diatomic metal -rare gas van der Waals complexes, as illustrated by recent representative studies involving metals in a number of chemical groups (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17). With the resulting derived spectroscopic data, considerable information has been obtained on the attractive portions of the potential energy curves of the ground and excited electronic states.…”

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confidence: 99%

Bound–free B²Σ⁺ –X²Π, A²Σ⁺ emission in the BAr van der Waals complex

Hwang¹,

Dagdigian²,

Alexander³

1994

Can. J. Chem.

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This pnper is dedicated to Professor John C. Polclnyi on the occasion ofhis 65th birthday E m s o o~ HWANG, PAUL J. DAGDIGIAN, and MILLARD H. ALEXANDER. Can. J. Chem. 72, 821 (1994).Spectrally resolved bound-free fluorescence emission spectra for the excitation of several vibrational levels in the excited B 2x+ electronic state of the van der Waals molecule " B A~ are presented. This excited state emits to the ground X 2n and low-lying A 'z+ states, both of which correlate with the ground state atomic asymptote B(2p 2~) + Ar. Because of the large differences in equilibrium internuclear separations, the emission occurs mainly to the repulsive walls. In order to gain more information on this portion of the potential energy curves, the experimental emission spectra were compared with simulated spectra derived from ob initio calculated B-Ar interaction potentials. The simulated spectra reproduce the experimental spectra well if the lower-state potential energy curves are shifted slightly inward. This discrepancy is consistent with our previous observation that the a b irlitio calculations slightly overestimate the vibrationally averaged internuclear separation, which we determined experimentally. This reflects the difficulty of accurately calculating weak van der Waals interaction energies. Introduction Supersonic beam and laser spectroscopic methods have been extensively employed to observe transitions between bound vibrational levels of weakly bound diatomic metal -rare gas van der Waals complexes, as illustrated by recent representative studies involving metals in a number of chemical groups (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17). With the resulting derived spectroscopic data, considerable information has been obtained on the attractive portions of the potential energy curves of the ground and excited electronic states. It would also be interesting to extract similar information on the repulsive parts of these curves from analysis of continuum spectra.In a recent paper (17), we reported a collaborative experimental and theoretical study of the BAr van der Waals complex. This metal -rare gas complex contains the lightest element of the group 13 family and has a relatively small number of electrons so that accurate electronic structure calculations could be carried out for the ground and excited electronic states of this system. Similar all-electron calculations on other weakly bound metal -rare gas complexes have performed (1 8-2 1). A number of the complexes of heavier members of this series (AlRg, InRg) have been spectroscopically studied by other groups (1 1-16). In our study of BAr, we observed (17), using laser fluorescence excitation of a pulsed supersonic beam, a progression of

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“…The conclusion is that the Zn•Xe( 3 ⌺ 1 ) curve is sufficiently repulsive to cross the deeply bound Zn•Xe( 1 ⌸ 1 ) potential curve below the energies of all the Zn•Xe( 1 ⌸ 1 ,vЈ) vibrational levels FranckCondon excited, and probably on the inner wall of the 1 ⌸ 1 curve. 8,9 As first postulated by Breckenridge and Malmin, 10 collision-induced intersystem crossing of M(nsnp 1 P 1 ) states to M(nsnp 3 P J ) states is now thought 11 11,12 potentials of the Zn•RG diatomics, the role played by the two lattice vibrations, Q 2 and Q 3 , in the corresponding 1 A 1 / 3 E predissociative ISC mechanism of matrix-isolated atomic zinc will be examined in this paper. Before the ISC behavior of the Zn-RG matrix systems is examined, that occurring for the Zn•RG n clusters of relevance to the matrix work will be treated.…”

Section: Introductionmentioning

confidence: 76%

“…However, ''action'' spectra, in which a second delayed laser pulse is tuned to a Zn( 3 P J ) atomic transition, allowed characterization of the Zn•Xe( 1 ⌸ 1 ) potential curve. 8 The lifetime of the excited 1 ⌸ 1 state of the half-collision Zn•Xe complex has been determined 8 to be 6 ps from linewidth measurements made in the action spectra. The conclusion is that the Zn•Xe( 3 ⌺ 1 ) curve is sufficiently repulsive to cross the deeply bound Zn•Xe( 1 ⌸ 1 ) potential curve below the energies of all the Zn•Xe( 1 ⌸ 1 ,vЈ) vibrational levels FranckCondon excited, and probably on the inner wall of the 1 ⌸ 1 curve.…”

Section: Introductionmentioning

confidence: 99%

A pair potentials study of matrix-isolated atomic zinc. II. Intersystem crossing in rare-gas clusters and matrices

Breckenridge

Morse

McCaffrey

1998

The Journal of Chemical Physics

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The mechanism of 4p 1 P 1 →4p 3 P J intersystem crossing ͑ISC͒ following excitation of the 4p 1 P 1 level of matrix-isolated atomic zinc is investigated using a pair potentials approach. This is achieved by extending earlier ISC calculations on the Zn•RG 2 and Zn•RG 3 complexes to the square planar Zn•RG 4 and square pyramidal Zn•RG 5 species which are the building blocks of the Zn•RG 18 cluster used to represent the isolation of atomic zinc in the substitutional site of a solid rare-gas host. ISC predictions in these clusters are based on whether crossing of the strongly bound 1 A 1 states, having a 4p 1 P 1 atomic asymptote, occurs with the repulsive 3 E states correlating with the 4p 3 P J atomic level of atomic zinc. Predictions based on 1 A 1 / 3 E curve crossings for 3 E states generated with the calculated ab initio points for the Zn•RG 3 ⌺(p z ) states do not agree with matrix observations. Based on similar overestimation of ISC in the Zn•RG diatomics, less repulsive Zn•RG 3 ⌺(p z ) potential curves are used resulting in excellent agreement between theory and observations in the Zn-RG matrix systems. 1 A 1 / 3 E curve crossings do not occur in the Zn-Ar system which shows only singlet emission. Curve crossings are found for the Zn-Xe system which exhibits only triplet emission. The Zn-Kr system does not show a crossing of the body mode Q 2 , which exhibits a strong singlet emission at 258 nm while the waist mode Q 3 , does have a crossing, resulting in a weak singlet emission at 239 nm and a stronger triplet emission at 312 nm. The efficiency of ISC is determined from Landau-Zener estimates of the surface hopping probabilities between the 1 A 1 and the 3 E states. Differences in the application of this theory in the gas and solid phase are highlighted, indicating that the rapid dissipation of the excited-state energy which occurs in the solid must be included to obtain agreement with observations.

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Excitation of zinc(4s4p'P1) within the zinc-xenon van der Waals complex: effect of p-orbital alignment on the production of zinc (4s4p3Pj)

Cited by 52 publications

References 0 publications

Quenching of excited P11 state atomic zinc by molecular nitrogen: A matrix-isolation spectroscopy/quantum chemical calculation study

Quenching of excited P11 state atomic zinc by molecular nitrogen: A matrix-isolation spectroscopy/quantum chemical calculation study

Bound–free B²Σ⁺ –X²Π, A²Σ⁺ emission in the BAr van der Waals complex

A pair potentials study of matrix-isolated atomic zinc. II. Intersystem crossing in rare-gas clusters and matrices

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Excitation of zinc(4s4p'P1) within the zinc-xenon van der Waals complex: effect of p-orbital alignment on the production of zinc (4s4p3Pj)

Cited by 52 publications

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Quenching of excited P11 state atomic zinc by molecular nitrogen: A matrix-isolation spectroscopy/quantum chemical calculation study

Quenching of excited P11 state atomic zinc by molecular nitrogen: A matrix-isolation spectroscopy/quantum chemical calculation study

Bound–free B2Σ+ –X2Π, A2Σ+ emission in the BAr van der Waals complex

A pair potentials study of matrix-isolated atomic zinc. II. Intersystem crossing in rare-gas clusters and matrices

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Bound–free B²Σ⁺ –X²Π, A²Σ⁺ emission in the BAr van der Waals complex