Detection of the H 2 PS free radical by laser spectroscopy Robert Grimminger * , Dennis J. Clouthier * , and Riccardo Tarroni † * Department of Chemistry, University of Kentucky, Lexington KY † Dipartimento di Chimica Fisica ed Inorganica, Università di Bologna, 40136 Bologna, Italy
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Detection of the H 2 PS free radical by laser spectroscopy Robert Grimminger *, Dennis J. Clouthier *, and Riccardo Tarroni † * Department of Chemistry,
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Detection of the H2PS free radical by laser spectroscopy
Robert Grimminger*, Dennis J. Clouthier*, and Riccardo Tarroni†
*Department of Chemistry, University of Kentucky, Lexington KY†Dipartimento di Chimica Fisica ed Inorganica, Università di Bologna, 40136 Bologna, Italy
Why study H2PS?
Phosphorus?
Spin labels
Production of jet-cooled radicals
5% H2 in Ar
H2PS
Cl3PS (liq.)
3% H2 in Ar +3% D2 in Ar5% D2 in Ar
D2PSH2PSD2PSHDPS
Molecular orbitals of H2PS
A2 X~
π (12a′)
n (4a″)
π* (13a′)
A2 A~
A2 B~
Energy (cm-1) 0 4,600 20,800
Calculations done by Riccardo Tarroni using CCSD and CCSD-EOM using aug-cc-pV(T+d)Z basis
Calculated geometry for lowest electronic states
State r (PS) Å r (PH)Å (HPS)° (HPH)° (oop)°
X� 2A 1.979 1.402 109.0 99.8 59.7
A 2A 2.139 1.413 94.2 90.4 84.1
B� 2A 2.114 1.411 109.9 94.4 59.9
a
c
b
H
H
P Sθ
CCSD and CCSD-EOM using aug-cc-pV(T+d)Z basis
Low resolution LIF spectra
000
000
103
104
102
203
10
1043
10
1032 3
03
204 1
02043
10
1032
303
10
1043
2031
03
102
ν2 = PH sym. Bendν3 = PS stretchν4 = HPH wag
104
Calc. = CCSD and CCSD-EOM using aug-cc-pV(T+d)Z basis