the pure rotational spectrum of ticl + (x 3 r ) by velocity modulation spectroscopy dewayne t....
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The Pure Rotational Spectrum of TiCl+ (X3r) by Velocity Modulation Spectroscopy
DeWayne T. Halfen and Lucy M. Ziurys
Department of ChemistryDepartment of Astronomy
Steward ObservatoryArizona Radio Observatory
University of Arizona
June 21, 2004
Why Molecular Ions ?Why Molecular Ions ?
• Chemical Aspect– Organic intermediates
– Stratospheric chemistry
– Combustion chemistry
• Astronomical Aspect– Many molecular ions in
interstellar medium
• Radicals – Difficult to study– Few molecular ions studied at
high resolution
Ions Studied at High Resolution
H3+ CO+ CH +
SO+ HCO+ HOC+
H2D+ HCS+ N2H+
H3O+ CH2D+ HCNH+
HOCO+ H2COH+ HC3NH+
OH+ OH HCl+
ArH+ HBr+
• Neutral species dominate over ions
• Built a new spectrometer – uses Velocity Modulation– Ion selective technique
Velocity Modulation SpectrometerVelocity Modulation Spectrometer
Detector
RadiationSource
Gas Cell
Reactant
Characteristics of Velocity ModulationCharacteristics of Velocity Modulation
• Drift velocity of TiCl+
–
– E = 1.9 V/cm, (Ar) = 1.6411 Å3, (Ar-TiCl+) = 26.99 amu, T = 208 K, P = 50 mTorr
– vd = 458.8 m/s
• Doppler shift
–
– = 606 kHz at v0 = 396 GHz
• Line width: ~ 1300 kHz
• Modulation index = / = 0.46– Under-modulated at millimeter wavelengths
15.273
T
P
760876.13Ev
2/1d
c
vvδν d
0
413.38 413.40 413.42 413.44 413.46 413.48
Frequency (GHz)
Source Modulation
46Ti35Cl+ ( = 2)J = 38 39
Source Modulation
413.38 413.40 413.42 413.44 413.46 413.48
Frequency (GHz)
Velocity Modulation
46Ti35Cl+ ( = 2)J = 38 39
Velocity Modulation
412.76 412.78 412.80 412.82 412.84
Frequency (GHz)
Source Modulation
48Ti35Cl ( = 7/2)J = 41.5 42.5
Source Modulation
412.76 412.78 412.80 412.82 412.84
Frequency (GHz)
Velocity Modulation
48Ti35Cl ( = 7/2)J = 41.5 42.5
Velocity Modulation
382.56 382.58 382.60 382.62 382.64
Frequency (GHz)
Source Modulation
V35Cl ( = 0e)J = 38 39
Source Modulation
382.56 382.58 382.60 382.62 382.64
Frequency (GHz)
Velocity Modulation
V35Cl ( = 0e)J = 38 39
Velocity Modulation
• <5% leakage of neutral signals in VM mode
Using Velocity ModulationUsing Velocity Modulation
• Use velocity modulation to distinguish neutrals from ions
Past Studies of TiCl+Past Studies of TiCl+
• Balfour & Chandrasekhar (1990)– First observed visible spectrum
• Kaledin & Heaven (1995,1997a,1997b) – Predicted X3r & confirmed using laser absorption
• Focsa et al. (1997a,1997b,1998,1999)– Used laser absorption/velocity modulation to measure several
electronic transitions
– Found that the = 2 & 3 subbands of X3r perturbed by 3r state
– Established spectroscopic constants for each state
Gas-Phase Synthesis of TiCl+Gas-Phase Synthesis of TiCl+
• Add TiCl4
– Pressure: <1 mTorr
• 20 mTorr Ar gas also added
• AC discharge – 200 W at 600
Energy Level Diagram for TiCl+Energy Level Diagram for TiCl+
• 3r ground state– Two unpaired 3d electrons
• J = L + S
• Spin-orbit and spin-spin interactions– &
• Omega ladders– = 2, 3, 4
– J ≥
• A3r state close in energy– Perturbs = 2 & 3 ladders
SLAH so SSH ss
0
100
200
300
400
500
600
700
En
erg
y (
cm
-1)
A3r
= 4
= 3
= 2: v = 0
= 1
= 2
= 3
X3r
395.945 395.965395.64 395.66Frequency (GHz)
396.095 396.115
48Ti35Cl+ (X3r): J = 37 38 = 2
= 4
= 3
Source Modulation
395.945 395.965395.640 395.660Frequency (GHz)
396.095 396.115
48Ti35Cl+ (X3r): J = 37 38 = 2
= 4 = 3
Velocity ModulationVelocity Modulation
392 393 394 395 396Frequency (GHz)
TiCl+ (X3r) = 2
= 3
= 4
48Ti35Cl+
J = 37 38
46Ti35Cl+
J = 36 37
48Ti37Cl+
J = 38 39
Rotational Spectrum of TiCl+Rotational Spectrum of TiCl+
• Fine structure components shifted from normal pattern
• TiCl+ confirmed by VM– S/N down by
factor of 4
• Measured 37Cl, 46Ti isotopomers in natural abundance
• Measured 10 rotational transitions of 48Ti35Cl+, 48Ti37Cl+, & 46Ti35Cl+
J J obs obs - calc J J obs obs - calc
30 31 2 322927.414 -0.015 35 36 2 374883.903 -0.009
3 323297.905 -0.089 3 375315.282 0.021
4 323156.037 -0.081 4 375163.298 0.063
31 32 2 333322.960 0.013 36 37 2 385268.555 -0.001
3 333705.663 0.028 3 385712.131 0.015
4 333561.278 -0.035 4 385558.787 0.053
32 33 2 343716.434 0.015 37 38 2 395650.832 -0.001
3 344111.266 0.020 3 396106.617 -0.007
4 343964.669 -0.011 4 395952.103 0.025
33 34 2 354107.777 -0.003 38 39 2 406030.676 -0.003
3 354514.788 0.025 3 406498.708 -0.014
4 354366.190 0.029 4 406343.266 -0.003
34 35 2 364496.962 -0.003 39 40 2 416408.036 0.006
3 364916.143 0.021 3 416888.324 -0.021
4 364765.753 0.055 4 416732.131 -0.099
Rest Frequencies of 48Ti35Cl+ (X3r)Rest Frequencies of 48Ti35Cl+ (X3r)
Spectroscopic Analysis of TiCl+Spectroscopic Analysis of TiCl+
•
• Determined spectroscopic constants for TiCl+
sssoroteff HHHH
48Ti35Cl+
Parameter MMW Optical
B 5216.6676(21) 5226.07(54)
D 0.00256353(78) 0.002728(45)
A 1900000 a 1904570(80)
AD 2.7834(89) -0.489(54)
AH 6.308(36) x 10-5
4404278(5000) 11030(180)
D -18.071(46) 0.507(18)
H -1.000 x 10-5 a
rms 0.037 a Held Fixed
• Rotational constants agree
• Fine structure parameters different– Different analysis
methods
• reflects large perturbation from A3r state
TiCl vs. TiCl+TiCl vs. TiCl+
• Relative intensities of TiCl vs. TiCl+ very similar
• Neutral only ~1.5x stronger than ion
• Ions usually very small fraction of plasma
• TiCl4 produces ions well
406.023 406.043
-0.5
0.0
0.5
1.0
Frequency (GHz)393.456391.298
-0.5
0.0
0.5
1.0
394.554392.375
406.334 406.354 406.491 406.511
= 3 = 4
= 2
48Ti35Cl (X4r): J = 39.5 40.5
48Ti35Cl+ (X3r): J = 38 39
*
= 3/2
= 5/2
= 7/2 = 9/2In
tens
ity
(mV
)In
tens
ity
(mV
)
Future WorkFuture Work
408.78 408.80 408.82 408.84 408.86
Frequency (GHz)
TiN (X2+)N = 10 11
J = 10.5 11.5
J = 9.5 10.5
• Measure spectra of more titanium species & molecular ions– TiC (X3), TiN+ (X1+), TiO+ (X2r), TiF+ (X3r)
411.39 411.41 411.43 411.45 411.47
Frequency (GHz)
TiO (X3r)
J = 12 13 = 1e/f
* *
• VCl - TH11
• VCl+ - TH12