A theoretical study of the electronic spectroscopy of the SiF3 radical

FR Manby; RP Tuckett; PJ Knowles

A theoretical study of the electronic spectroscopy of the SiF₃ radical

FR Manby, RP Tuckett^*, PJ Knowles

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article (Academic Journal) › peer-review

Abstract

A recent vacuum-UV fluorescence spectrum of SiF4 [H. Biehl, K.J. Boyle, D.P. Seccombe, D.M. Smith, R.P. Tuckett, K.R. Yoxall, H. Baumgartel, H.W. Jochims, J. Chem. Phys. 107 (1997) 720] has yielded information about the decay of electronically excited states of neutral fragments and the parent molecular cation. Emission in the visible region (lambda > 380 nm) has been observed for an excitation energy of 13.0 eV with a lifetime of 3.9 ns, but the emitter was not assigned. Ab initio CASSCF calculations show that the observed emission is due to the (A) over tilde (2)A(1)-(X) over tilde (2)A(1) transition in the SiF3 radical. The experimental lifetime, however, is too short to be attributed to this radiative process. We suggest that the lifetime is dominated by rapid internal conversion of SiF3 (A) over tilde (2)A(1) into high vibrational levels of the ground state. (C) 2001 Elsevier Science B.V. All rights reserved.

Translated title of the contribution	A theoretical study of the electronic spectroscopy of the SiF₃ radical
Original language	English
Pages (from-to)	599-602
Number of pages	4
Journal	Chemical Physics Letters
Volume	342
Issue number	5-6
Publication status	Published - 20 Jul 2001

Keywords

CORRELATED MOLECULAR CALCULATIONS
CHEMI-LUMINESCENCE
GAUSSIAN-BASIS SETS
ARGON
SILICON
SCF METHOD
EMISSION-SPECTRA
UV
CF3 RADICALS

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@article{704df5b8b8d04816a2d177ce1dd6253a,

title = "A theoretical study of the electronic spectroscopy of the SiF3 radical",

abstract = "A recent vacuum-UV fluorescence spectrum of SiF4 [H. Biehl, K.J. Boyle, D.P. Seccombe, D.M. Smith, R.P. Tuckett, K.R. Yoxall, H. Baumgartel, H.W. Jochims, J. Chem. Phys. 107 (1997) 720] has yielded information about the decay of electronically excited states of neutral fragments and the parent molecular cation. Emission in the visible region (lambda > 380 nm) has been observed for an excitation energy of 13.0 eV with a lifetime of 3.9 ns, but the emitter was not assigned. Ab initio CASSCF calculations show that the observed emission is due to the (A) over tilde (2)A(1)-(X) over tilde (2)A(1) transition in the SiF3 radical. The experimental lifetime, however, is too short to be attributed to this radiative process. We suggest that the lifetime is dominated by rapid internal conversion of SiF3 (A) over tilde (2)A(1) into high vibrational levels of the ground state. (C) 2001 Elsevier Science B.V. All rights reserved.",

keywords = "CORRELATED MOLECULAR CALCULATIONS, CHEMI-LUMINESCENCE, GAUSSIAN-BASIS SETS, ARGON, SILICON, SCF METHOD, EMISSION-SPECTRA, UV, CF3 RADICALS",

author = "FR Manby and RP Tuckett and PJ Knowles",

year = "2001",

month = jul,

day = "20",

language = "English",

volume = "342",

pages = "599--602",

journal = "Chemical Physics Letters",

issn = "0009-2614",

publisher = "North-Holland Publishing Company",

number = "5-6",

}

TY - JOUR

T1 - A theoretical study of the electronic spectroscopy of the SiF3 radical

AU - Manby, FR

AU - Tuckett, RP

AU - Knowles, PJ

PY - 2001/7/20

Y1 - 2001/7/20

N2 - A recent vacuum-UV fluorescence spectrum of SiF4 [H. Biehl, K.J. Boyle, D.P. Seccombe, D.M. Smith, R.P. Tuckett, K.R. Yoxall, H. Baumgartel, H.W. Jochims, J. Chem. Phys. 107 (1997) 720] has yielded information about the decay of electronically excited states of neutral fragments and the parent molecular cation. Emission in the visible region (lambda > 380 nm) has been observed for an excitation energy of 13.0 eV with a lifetime of 3.9 ns, but the emitter was not assigned. Ab initio CASSCF calculations show that the observed emission is due to the (A) over tilde (2)A(1)-(X) over tilde (2)A(1) transition in the SiF3 radical. The experimental lifetime, however, is too short to be attributed to this radiative process. We suggest that the lifetime is dominated by rapid internal conversion of SiF3 (A) over tilde (2)A(1) into high vibrational levels of the ground state. (C) 2001 Elsevier Science B.V. All rights reserved.

AB - A recent vacuum-UV fluorescence spectrum of SiF4 [H. Biehl, K.J. Boyle, D.P. Seccombe, D.M. Smith, R.P. Tuckett, K.R. Yoxall, H. Baumgartel, H.W. Jochims, J. Chem. Phys. 107 (1997) 720] has yielded information about the decay of electronically excited states of neutral fragments and the parent molecular cation. Emission in the visible region (lambda > 380 nm) has been observed for an excitation energy of 13.0 eV with a lifetime of 3.9 ns, but the emitter was not assigned. Ab initio CASSCF calculations show that the observed emission is due to the (A) over tilde (2)A(1)-(X) over tilde (2)A(1) transition in the SiF3 radical. The experimental lifetime, however, is too short to be attributed to this radiative process. We suggest that the lifetime is dominated by rapid internal conversion of SiF3 (A) over tilde (2)A(1) into high vibrational levels of the ground state. (C) 2001 Elsevier Science B.V. All rights reserved.

KW - CORRELATED MOLECULAR CALCULATIONS

KW - CHEMI-LUMINESCENCE

KW - GAUSSIAN-BASIS SETS

KW - ARGON

KW - SILICON

KW - SCF METHOD

KW - EMISSION-SPECTRA

KW - UV

KW - CF3 RADICALS

M3 - Article (Academic Journal)

SN - 0009-2614

VL - 342

SP - 599

EP - 602

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 5-6